Benzotriazole UV absorbers having enhanced durability

ABSTRACT

Benzotriazole UV absorbers which are substituted at the 5-position of the benzo ring by an electron withdrawing group exhibit enhanced durability and very low loss rates when incorporated into automotive coatings.

[0001] This application claims the benefit under 35 USC 119(e) of U.S.application Ser. No. 08/745,146, filed on Nov. 7, 1996, and convertedinto a Provisional Application by petition under 37 CFR 1.53(b)(2)(ii),filed on May 23, 1997, and granted on Aug. 7, 1997.

[0002] Benzotriazole UV absorbers being substituted in the benzo ring byelectron withdrawing moieties exhibit enhanced durability and low lossrates when incorporated into automotive coatings.

BACKGROUND OF THE INVENTION

[0003] The benzotriazoles have long been an important class of UVabsorbers and have gained wide commercial importance and acceptance formany industrial applications. The prior art is replete with referencesto their manufacture and utility. However, as requirements become evermore stringent and demanding, the search for still more stable anddurable benzotriazoles continues. The gradual phase out of HAPSsolvents, such as xylene, because of environmental concerns and theirreplacement with non-HAPS solvents, such as esters, ethers or ketones,and increased durability requirements for automotive coatings make thissearch more urgent. Indeed, the automotive industry is most concernedabout UVA losses from automotive paints and coatings as seen in thepublication by J. L. Gerlock et al., Proc. 36th Annual Tech. Sym.(Cleveland Coating Society), May 18, 1993.

[0004] Vysokomol Soedin, Ser. A, 18(3), 553 (1976) describes the lineardependence of hydrogen bond strength and photostability inbenzotriazoles.

[0005] J. E. Pickett et al., Angew. Makromol. Chem. 232, 229 (1995)describe the photodegradation of benzotriazole UV absorbers inpoly(methyl methacrylate) films. Structural variation generally causedonly small differences in the rates of degradation unless thesubstitution disrupted the intramolecular hydrogen bonds which arecritical for stability. Pickett et al. did not test any benzotriazolescontaining both electron withdrawing and electron donating groups as inthe instant invention.

[0006] The prior art leads one to the conclusion that strengthening thehydrogen bond leads to a more stable benzotriazole, but does not teachhow this can be accomplished. The instant invention disclosesbenzotriazoles which exhibit enhanced durability, but surprisingly thisenhanced durability is not always related to greater hydrogen bondstrength. Indeed, compounds with enhanced durability often have weaker,not stronger hydrogen bonds

[0007] U.S. Pat. Nos. 4,226,763; 4,278,589; 4,315,848; 4,275,004;4,347,180; 5,554,760; 5,563,242; 5,574,166 and 5,607,987 describeselected benzotriazoles, substituted in the 3-position of thehydroxyphenyl ring by an α-cumyl group, which show very good durabilityin automotive coatings. These benzotriazoles represent the present stateof the art. The instant invention is directed at preparingbenzotriazoles which exhibit still better durability and low loss ratesfrom the prior art benzotriazoles.

[0008] U.S. Pat. Nos. 5,278,314; 5,280,124; 5,436,349 and 5,516,914describe red-shifted benzotriazoles. These benzotriazoles aresubstituted in the 5-position of the benzo ring by thio ethers,alkylsulfonyl or phenylsulfonyl moieties. Red-shifting thebenzotriazoles is desirable for spectral reasons. A group at the5-position which is also electron withdrawing provides additionalbenefits in low loss rates and durability as found in the instantinvention.

DETAILS OF THE DISCLOSURE

[0009] The instant invention pertains to benzotriazole UV absorbershaving enhanced stability and durability and a low loss rate whenincorporated into automotive coatings.

[0010] More particularly, the instant invention pertains to a coatingcomposition, stabilized with a benzotriazole, which benzotriazoleexhibits enhanced durability and a low loss rate when incorporated insaid coating, which composition comprises

[0011] (a) a resin selected from the group consisting of a thermosetacrylic melamine resin, an acrylic urethane resin, an epoxy carboxyresin, a silane modified acrylic melamine, an acrylic resin withcarbamate pendant groups crosslinked with melamine or an acrylic polyolresin crosslinked with melamine containing carbamate groups, and

[0012] (b) 0.01 to 5% by weight, based on resin solids, of abenzotriazole of formula A, B, C or D

[0013] wherein

[0014] G₁, G₂ or T is an electron withdrawing radical,

[0015] G₁ is hydrogen or halogen,

[0016] G₂ is halogen, nitro, cyano, R₃SO—, R₃SO₂—, —COOG₃, CF₃—,—P(O)(C₆H₅)₂, —CO—G₃, —CO—NH—G₃, —CO—N(G₃)₂, —N(G₃)—CO—G₃,

[0017] G₃ is hydrogen, straight or branched chain alkyl of 1 to 24carbon atoms, straight of branched chain alkenyl of 2 to 18 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,

[0018] R₁ is hydrogen, straight or branched chain alkyl of 1 to 24carbon atoms, straight of branched chain alkenyl of 2 to 18 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,

[0019] R₂ is straight or branched alkyl chain of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkylof 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; or R₂ is hydroxyl or —OR₄ where R₄ isstraight or branched chain alkyl of 1 to 24 carbon atoms; or said alkylsubstituted by one or more —OH, —OCO—R₁₁, —OR₄, —NCO or —NH₂ groups ormixtures thereof; or said alkyl or said alkenyl interrupted by one ormore —O—, —NH— or —NR₄— groups or mixtures thereof and which can beunsubstituted or substituted by one or more —OH, —OR₄ or —NH₂ groups ormixtures thereof; or R₂ is —SR₃, —NHR₃ or —N(R₃)₂; or R₂ is

—(CH₂)_(m)—CO—X—(Z)_(p)—Y—R₁₅

[0020] wherein

[0021] X is —O— or —N(R₁₆)—,

[0022] Y is —O— or —N(R₁₇)—,

[0023] Z is C₂-C₁₂-alkylene, C₄-C₁₂-alkylene interrupted by one to threenitrogen atoms, oxygen atoms or a mixture thereof, or isC₃-C₁₂-alkylene, butenylene, butynylene, cyclohexylene or phenylene,each substituted by a hydroxyl group,

[0024] m is zero, 1 or 2,

[0025] p is 1, or p is also zero when X and Y are —N(R₁₆)— and —N(R₁₇)—,respectively,

[0026] R₁₅ is a group —CO—C(R₁₈)═C(H)R₁₉ or, when Y is —N(R₁₇)—, formstogether with R₁₇ a group —CO—CH═CH—CO—, wherein R₁₈ is hydrogen ormethyl, and R₁₉ is hydrogen, methyl or —CO—X—R₂₀, wherein R₂₀ ishydrogen, C₁-C₁₂-alkyl or a group of the formula.

[0027] wherein the symbols R₁, R₃, X, Z, m and p have the meaningsdefined above, and R₁₆ and R₁₇ independently of one another arehydrogen, C₁-C₁₂-alkyl, C₃-C₁₂-alkyl interrupted by 1 to 3 oxygen atoms,or is cyclohexyl or C₇-C₁₅aralkyl, and R₁₆ together with R₁₇ in the casewhere Z is ethylene, also forms ethylene,

[0028] n is 1 or 2,

[0029] when n is 1, R₅ is Cl, OR₆ or NR₇R₈, or

[0030] R₅ is —PO(OR₁₂)₂, —OSi(R₁₁)₃ or —OCO—R₁₁, or straight or branchedchain C₁-C₂₄alkyl which is interrupted by —O—, —S— or —NR₁₁ and whichcan be unsubstituted or substituted by —OH or —OCO—R₁₁, C₅-C₁₂cycloalkyl which is unsubstituted or substituted by —OH, straight chainor branched C_(2-C) ₁₈alkenyl which is unsubstituted or substituted by—OH, C₇-C₁₅aralkyl, —CH₂—CHOH—R₁₃ or glycidyl,

[0031] R₆ is hydrogen, straight or branched chain C₁-C₂₄alkyl which isunsubstituted or substituted by one or more OH, OR₄ or NH₂ groups, or—OR₆ is —(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OR₂, where w is 1 to 12 andR₂₁ is alkyl of 1 to 12 carbon atoms,

[0032] R₇ and R₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms, straight or branched chain C₃-C₁₈alkyl which is interrupted by—O—, —S— or —NR₁₁, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl,or R₇ and R₈ together with the N atom are a pyrrolidine, piperidine,piperazine or morpholine ring,

[0033] when n is 2, R₅ is one of divalent radicals —O—R₉—O— or—N(R₁₁)—R₁₀—N(R₁₁)—,

[0034] R₉ is C₂-C₈alkylene, C₄-C₈alkenylene, C₄alkynylene,cyclohexylene, straight or branched chain C₄-C₁₀alkylene which isinterrupted by —O— or by —CH₂—CHOH—CH₂—O—R₁₄—O—CH₂—CHOH—CH₂—,

[0035] R₁₀ being straight or branched chain C₂-C₁₂alkylene which may beinterrupted by —O—, cyclohexylene, or

[0036] or R₁₀ and R₁₁ with the two nitrogen atoms form a piperazinering,

[0037] R₁₄ is straight or branched chain C₂-C₈alkylene, straight orbranched chain C₄-C₁₀alkylene which is interrupted by —O—,cycloalkylene, arylene or

[0038] where R₇ and R₈ are independently hydrogen, alkyl of 1 to 18carbon atoms or R₇ and R₈ together are alkylene of 4 to 6 carbon atoms,3-oxapentamethylene, 3-iminopentamethylene or3-methyliminopentamethylene,

[0039] R₁₁ is hydrogen, straight or branched chain C₁-C₁₈alkyl,C₅-C₁₂cycloalkyl, straight or branched chain C₃-C₈alkenyl, C₆-C₁₄aryl orC₇-C₁₅aralkyl,

[0040] R₁₂ is straight or branched chain C₁-C₁₈alkyl, straight orbranched chain C₃-C₁₈alkenyl, C₅-C₁₀cycloalkyl, C₆-C₁₆aryl orC₇-C₁₅aralkyl,

[0041] R₁₃ is H, straight chain or branched C₁-C₁₈alkyl which issubstituted by —PO(OR₁₂)₂, phenyl which is unsubstituted or substitutedby OH, C₇-C₁₅aralkyl or —CH₂OR₁₂,

[0042] R₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10carbon atoms or said aryl substituted by one or two alkyl of 1 to 4carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where theperfluoroalkyl moiety is of 6 to 16 carbon atoms,

[0043] L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and

[0044] T is —SO—, —SO₂—, —SO—E—SO—, —SO₂—E—SO₂—, —CO—, —CO—E—CO—,—COO—E—OCO—, —CO—NG₃—E—NG₃—CO— or —NG₃—CO—E—CO—NG₃—,

[0045] where E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5to 12 carbon atoms, or alkylene interrupted or terminated bycyclohexylene of 8 to 12 carbon atoms, which benzotriazole exhibitsenhanced durability and low loss rate values when the coating is exposedto actinic radiation as witnessed by a loss of less than 0.22 absorbanceunits after exposure for 1200 hours, or less than 0.27 absorbance unitsafter 1500 hours exposure, or less than 0.40 absorbance units after 2500hours exposure in a Xenon-Arc Weather-Ometer.

[0046] Preferably, component (b) is a compound of formula A′

[0047] wherein

[0048] G₂ is fluoro, chloro, cyano, R₃SO₂—, CF₃—, —CO—G₃, —COO—G₃ or—CO—N(G₃)₂

[0049] G₃ is alkyl of 1 to 12 carbon atoms,

[0050] R₁ is hydrogen, alkyl of 1 to 12 carbon atoms, phenyl,phenylalkyl of 7 to 15 carbon atoms or said phenyl or said phenylalkylsubstituted on the phenyl ring by 1 or 2 alkyl groups of 1 to 4 carbonatoms,

[0051] R₂ is alkyl of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to15 carbon atoms or —CH₂CH₂COOG₄ where G₄ is hydrogen, alkyl of 1 to 24carbon atoms or said alkyl substituted by OH, interrupted by one to six—O— atoms or both substituted by OH and interrupted by one to six —O—atoms, and

[0052] R₃ is alkyl of 1 to 18 carbon atom, aryl of 6 to 10 carbon atomsor said aryl substituted one or two alkyl of 1 to 4 carbon atoms.

[0053] Most preferably, in the compound of formula A′,

[0054] G₂ is fluoro, chloro, cyano, R₃SO₂—, CF₃—, —COO—G₃ or —CO—N(G₃)₂,

[0055] G₃ is alkyl of 1 to 8 carbon atoms,

[0056] R₁ is hydrogen, phenyl or α-cumyl,

[0057] R₂ is alkyl of 4 to 12 carbon atoms or phenyl, and

[0058] R₃ is phenyl or alkyl of 8 to 12 carbon atoms.

[0059] Especially preferred are the compounds of formula A′ where G₂ isphenyl—SO₂—, octyl-SO₂—, fluoro or CF₃—, R₁ is α-cumyl or phenyl, and R₂is tert-butyl or tert-octyl.

[0060] Preferably, the resin is a thermoset acrylic melamine resin or anacrylic urethane resin.

[0061] Examples of these various radicals are as follow:

[0062] When any of R₁ to R₂₁ is alkyl, such groups are, for example,methyl, ethyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,tert-amyl, 2-ethylhexyl, tert-octyl, lauryl, tert-dodecyl, tridecyl,n-hexadecyl, n-octadecyl and eicosyl; when any of said radicals isalkenyl, such groups are, for example, allyl or oleyl; when any of saidradicals is cycloalkyl, such groups are, for example, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl; when any of saidradicals are phenylalkyl, such groups are, for example, benzyl,phenethyl, α-methylbenzyl and α,α-dimethylbenzyl; and when any of saidradicals is aryl, they are, for example, phenyl, naphthyl, or whensubstituted by alkyl are, for example, tolyl and xylyl. When R₆ is alkylsubstituted by one or more —O— groups and/or substituted by one or more—OH, the —OR₆ moiety can be —(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OR₂₁ wherew is 1 to 12 and R₂₁ is alkyl of 1 to 12 carbon atoms, for example.

[0063] When E is alkylene, it is, for example, ethylene, tetramethylene,hexamethylene, 2-methyl-1,4-tetramethylene, hexamethylene,octamethylene, decamethylene and dodecamethylene; when E iscycloalkylene, it is, for example, cyclopentylene, cyclohexylene,cycloheptylene, cyclooctylene and cyclododecylene; and when E isalkylene interrupted or terminated by cyclohexylene, it is , forexample, the saturated diyl radical derived from limonene, herein calleddihydrolimonenediyl.

[0064] A further preferred embodiment of the invention is a compound offormula III in which R₁ is tert-butyl, n is 1, R₃ is phenyl and R₅ is—OR₆ where R₆ is a straight chain or substituted octyl group. Yetanother preferred embodiment of the instant invention is a compound offormula C where n is 2, R₁ is tert-butyl, R₃ is phenyl, and R₅ is—O—R₉—O— where R₉ is C₂-C₂₄alkylene interrupted by —O— or by—CH₂—CHOH—CH₂—O—R₁₄—O—CH₂—CHOH—CH₂—.

[0065] When E is alkylene, it is, for example, ethylene, tetramethylene,hexamethylene, 2-methyl-1,4-tetramethylene, hexamethylene,octamethylene, decamethylene and dodecamethylene; when E iscycloalkylene, it is, for example, cyclopentylene, cyclohexylene,cycloheptylene, cyclooctylene and cyclododecylene; and when E isalkylene interrupted or terminated by cyclohexylene, it is, for example,the saturated diyl radical derived from limonene, herein calleddihydrolimonenediyl.

[0066] When the instant compounds contain a free carboxyl moiety whereR₂ is —CH₂CH₂COOR₆ where R₆ is hydrogen, the alkali metal or amine saltsof said acids are also contemplated as part of this invention allowingsuch UV absorbers to be used in aqueous systems due to the enhancedwater solubility of such instant compounds.

[0067] R₆, R₇ and R₈ can be the following C₃-C₁₈alkyl radicals which areinterrupted by —O—, —S—, or —NR₁₁— and can be substituted by OH:methoxyethyl, ethoxyethyl, butoxyethyl, butoxypropyl, methylthioethyl,CH₃OCH₂CH₂OCH₂CH₂—, CH₃CH₂OCH₂CH₂OCH₂CH₂—, C₄H₉OCH₂CH₂OCH₂CH₂—,ethylthiopropyl, octylthiopropyl, dodecyloxypropyl, 2-hydroxyethyl,2-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, —CH₂CH₂—NH—C₄H₉,—CH₂CH₂CH₂NH—C₈H₁₇ and —CH₂CH₂CH₂—N(CH₃)—CH₂CH(C₂H₅)C₄H₉,

[0068] R₆, R₇, R₈, R₁₁ and R₁₂ can be the following C₅-C₁₂cycloalkylradicals: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl orcyclodecyl. In the case of R₆, the radical can also be substituted by—OH.

[0069] R₇, R₈ and R₁₁, can be the following alkenyl radicals: allyl,methallyl, 2-n-hexenyl or 4-n-octenyl.

[0070] When R₆ is alkenyl, it can have the same meaning as R₇, R₈ andR₁₁ as alkenyl radicals, but it can also be —CH═CH₂, n-undec-10-enyl orn-octadec-9-enyl, and it is also possible for the radical R₆ to besubstituted by —OH.

[0071] R₇ and R₈ can be the following C₇-C₁₅aralkyl radicals: benzyl,α-phenethyl, 2-phenethyl or 4-tert-butylbenzyl.

[0072] When R₁₁, R₁₃ or R₁₂ are aralkyl, they can, independently of oneanother, have the same meaning as R₇ or R₈.

[0073] Independently of one another, R₇, R₈ and R₁₁ can be the followingC₆-C₁₄ aryl radicals: phenyl, α-naphthyl or β-naphthyl.

[0074] When R₇ and R₈ are C₁-C₃ hydroxyalkyl, they can be the followingradicals: hydroxymethyl, 2-hydroxyethyl or 2-hydroxypropyl.

[0075] As C₂-C₈ alkylene, R₉ and R₁₄ can be the following radicals:ethylene, propylene, butylene, hexylene or octylene.

[0076] As alkylene, R₁₀ can be the same radicals, but can, in addition,also be higher-molecular groups such as decylene or dodecylene.

[0077] When R₉ is a C₄-C₈alkenylene radical, the following is an exampleof a suitable group: butenylene.

[0078] In the case of R₉ and R₁₄, suitable straight or branched chainC₄-C₁₀alkylene groups which are interrupted by —O— are the followinggroups: —CH₂CH₂OCH₂CH₂—,—CH(CH₃)—CH₂—O—CH₂—CH(CH₃)—CH₂CH₂OCH₂CH₂OCH₂CH₂— and—CH₂CH₂OCH₂CH₂OCH₂CH₂OCH₂CH₂—.

[0079] When R₁₄ is a cycloalkylene radical, the following groups areembraced: 1,3-cyclohexylene and 1,4-cyclohexylene.

[0080] When R₁₄ is arylene, this can be, specifically, the followinggroups: 1,3-phenylene or 1,4-phenylene.

[0081] As C₂-C₁₂-alkylene, Z is a straight or branched chain. It is forexample: ethylene, propylene, tetramethylene, hexamethylene,octamethylene, dodecamethylene, 1,1-ethylidene, 2,2-propylidene,2,2-amylidene or 2-ethylhexamethylene. C₂-C₆-alkylene groups arepreferred.

[0082] When Z is C₄-C₁₂-alkylene which is interrupted by oxygen, it isfor example: —CH₂—CH₂—O—CH₂—CH₂—, —CH₂—CH₂—O—CH₂—CH₂—CH₂,CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂ or —CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂—,and, when alkylene is interrupted by nitrogen, a group —N(R₁₆)— ismeant, where R₁₆ is as defined in the foregoing, for example—CH₂—CH₂—NH—CH₂—CH₂—CH₂—CH₂, —CH₂—CH₂—CH₂—NH—(CH₂)₈— or—CH₂CH₂—CH₂—N(CH₃—CH₂—CH(C₂H₅)(CH₂)₄—.

[0083] As C₃-C₁₂-alkylene substituted by a hydroxyl group, Z is2-hydroxytetramethylene, 2-hydroxyhexamethylene and, in particular,2-hydroxytrimethylene.

[0084] As cyclohexylene, Z is for example 1,4-cyclohexylene and, inparticular, 1,2-cyclohexylene.

[0085] As phenylene, Z is for example m-phenylene or p-phenylene.

[0086] m can be zero, 1 or 2, but it is preferably 2.

[0087] p is preferably 1, but can also be zero if both X and Y are boundby way of nitrogen.

[0088] As C₁-C₈-alkyl, R₁ is for example: methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-amyl, n-nexyl,n-heptyl, n-octyl, 2-ethylhexyl or tert-octyl. Tert-butyl is preferred.

[0089] As C₁-C₁₂-alkyl, R₁₆ R₁₇ and R₂₀ can have the same meaning asthat given in the foregoing for R₁, and can additionally be straight orbranched-chain nonyl, decyl, undecyl, or dodecyl.

[0090] When R₁₆ and R₁₇ are alkyl interrupted by oxygen atoms, theexamples which apply are the same as those described in the foregoingfor Z.

[0091] Examples for R₁₆ and R₁₇ as aralkyl are: benzyl, α-methylbenzyl,1-phenylethyl, α,α-dimethylbenzyl or 1-phenylpropyl.

[0092] If Z is ethylene, R₁₆ and R₁₇ together can likewise formethylene, which is equivalent to a bridging over by way of a piperazinegroup.

[0093] When Y is a group —N(R₁₇)—, R₁₅ and R₁₇ together make up a group—CO—CH═CH—CO—, and thus form the substituent

[0094] on the group —X—(Z)_(p)—.

[0095] The preferred meaning of R₁₅ is, however, —CO—C(R₁₈)═CHR₁₄, R₁₈and R₁₉ are preferably methyl and especially hydrogen.

[0096] R₂ is —CH₂—CH₂—CO—O—C(G)═CH₂ and G is hydrogen or methyl.

[0097] The instant invention also pertains to new benzotriazoles offormulas I, II, III or IV

[0098] wherein

[0099] G₁ is hydrogen or halogen,

[0100] G₂ is cyano, E₃SO—, E₃SO₂—, —COOG₃, CF₃—, —P(O)(C₆H₅)₂, —CO—G₃,—CO—NHG₃ or —CO—N(G₃)₂,

[0101] G₃ is straight or branched chain alkyl of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkylof 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4alkyl of 1 to 4 carbon atoms,

[0102] E₁ is hydrogen, phenylalkyl of 7 to 15 carbon atoms, phenyl, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4alkyl of 1 to 4 carbon atoms,

[0103] E₂ is straight or branched alkyl chain of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkylof 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; or E₂ is hydroxyl or —OE₄ where E₄ isstraight or branched chain alkyl of 1 to 24 carbon atoms; or said alkylsubstituted by one or more —OH, —OCO—E₁₁, —OE₄, —NCO or —NH₂ groups ormixtures thereof; or said alkyl or said alkenyl interrupted by one ormore —O—, —NH— or —NE₄— groups or mixtures thereof and which can beunsubstituted or substituted by one or more —OH, —OE₄ or —NH₂ groups ormixtures thereof; or E₂ is —SE₃, —NHE₃ or —N(E₃)₂; or E₂ is

—(CH₂)_(m)—CO—X—(Z)_(p)—Y—E₁₅

[0104] wherein

[0105] X is —O— or —N(E₁₆)—,

[0106] Y is —O— or —N(E₁₇)—,

[0107] Z is C₂-C₁₂-alkylene, C₄-C₁₂-alkylene interrupted by one to threenitrogen atoms, oxygen atoms or a mixture thereof, or isC₃-C₁₂-alkylene, butenylene, butynylene, cyclohexylene or phenylene,each substituted by a hydroxyl group,

[0108] m is zero, 1 or 2,

[0109] p is 1, or p is also zero when X and Y are —N(E₁₆)— and —N(E₁₇)—,respectively,

[0110] E₁₅ is a group —CO—C(E₁₈)═C(H)E₁₉ or, when Y is —N(E₁₇)—, formstogether with E₁₇ a group —CO—CH═CH—CO—, wherein E₁₈ is hydrogen ormethyl, and E₁₇ is hydrogen, methyl or —CO—X—E₂₀, wherein E₂₀ ishydrogen, C₁-C₁₂-alkyl or a group of the formula.

[0111] wherein the symbols E₁, G₂, X, Z, m and p have the meaningsdefined above, and E₁₆ and E₁₇ independently of one another arehydrogen, C₁-C₁₂-alkyl, C₃-C₁₂-alkyl interrupted by 1 to 3 oxygen atoms,or is cyclohexyl or C₇-C₁₅aralkyl, and E₁₆ together with E₁₇ in the casewhere Z is ethylene, also forms ethylene,

[0112] n is 1 or 2,

[0113] when n is 1, E₅ is Cl, OE₆ or NE₇E₈, or

[0114] E₅ is —PO(OE₁₂)₂, —OSi(E₁₁)₃ or —OCO—E₁₁, or straight or branchedchain C₁-C₂₄alkyl which is interrupted by —O—, —S— or —NE₁₁ and whichcan be unsubstituted or substituted by —OH or —OCO—E₁₁, C₅-C₁₂cycloalkyl which is unsubstituted or substituted by —OH, straight chainor branched C₂-C₁ ₈alkenyl which is unsubstituted or substituted by —OH,C₇-C₁₅aralkyl, —CH₂—CHOH—E₁₃ or glycidyl,

[0115] E₆ is hydrogen, straight or branched chain C₁-C₂₄alkyl which isunsubstituted or substituted by one or more OH, OE₄ or NH₂ groups, or—OE₆ is —(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OE₂₁where w is 1 to 12 and E₂₁is alkyl of 1 to 12 carbon atoms,

[0116] E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms, straight or branched chain C₃-C₁₈alkyl which is interrupted by—O—, —S— or —NE₁₁—, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl,or E₇ and E₈ together with the N atom are a pyrrolidine, piperidine,piperazine or morpholine ring,

[0117] when n is 2, E₅ is one of divalent radicals —O—E₉—O— or—N(R₁₁)—E₁₀—N(E₁₁)—,

[0118] E₉ is C₂-C₈alkylene, C₄-C₈alkenylene, C₄alkynylene,cyclohexylene, straight or branched chain C₄-C₁₀alkylene which isinterrupted by —O— or by —CH₂—CHOH—CH₂—O—E₁₄—O—CH₂—CHOH—CH₂—,

[0119] E₁₀ being straight or branched chain C₂-C₁₂alkylene which may beinterrupted by —O—, cyclohexylene, or

[0120] or E₁₀ and E₁₁ with the two nitrogen atoms form a piperazinering,

[0121] E₁₄ is straight or branched chain C₂-C₈alkylene, straight orbranched chain C₄-C₁₀alkylene which is interrupted by —O—,cycloalkylene, arylene or

[0122] where E₇ and E₈ are independently hydrogen, alkyl of 1 to 18carbon atoms or E₇ and E₈ together are alkylene of 4 to 6 carbon atoms,3-oxapentamethylene, 3-iminopentamethylene or3-methyliminopentamethylene,

[0123] E₁₁ is hydrogen, straight or branched chain C₁-C₁₈alkyl,C₅-C₁₂cycloalkyl, straight or branched chain C₃-C₈alkenyl, C₆-C₁₄aryl orC₇-C₁₅aralkyl,

[0124] E₁₂ is straight or branched chain C₁-C₁₈alkyl, straight orbranched chain C₃-C₁₈alkenyl, C₅-C₁₀cycloalkyl, C₆-C₁₆aryl orC₇-C₁₅aralkyl,

[0125] E₁₃ is H, straight chain or branched C₁-C₁₈alkyl which issubstituted by —PO(OR₁₂)₂, phenyl which is unsubstituted or substitutedby OH, C₇-C₁₅aralkyl or —CH₂OE₁₂,

[0126] E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10carbon atoms or said aryl substituted by one or two alkyl of 1 to 4carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where theperfluoroalkyl moiety is of 6 to 16 carbon atoms,

[0127] L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and

[0128] T is —SO—, —SO₂—, —SO—E—SO—, —SO₂—E—SO₂—, —CO—, —CO—E—CO—,—COO—E—OCO— or —CO—NG₅—E—NG₅—CO—,

[0129] where E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5to 12 carbon atoms, or alkylene interrupted or terminated bycyclohexylene of 8 to 12 carbon atoms;

[0130] G₅ is G₃ or hydrogen, and

[0131] with the proviso that E₁ is not phenylalkyl when G₂ is E₃SO— orE₃SO₂—.

[0132] Preferably, the new benzotriazole is a compound of formula I′

[0133] wherein

[0134] G₂ is cyano, E₃SO₂—, CF₃—, —COO—G₃—CO—NHG₃ or —CO—N(G₃)₂,

[0135] G₃ is alkyl of 1 to 12 carbon atoms,

[0136] E₁ is hydrogen, phenyl, phenylalkyl of 7 to 15 carbon atoms orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 or 2alkyl groups of 1 to 4 carbon atoms,

[0137] E₂ is alkyl of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to15 carbon atoms or —CH₂CH₂COOG₄ where G₄ is hydrogen, alkyl of 1 to 24carbon atoms or said alkyl substituted by OH, interrupted by one to six—O— atoms or both substituted by OH and interrupted by one to six —O—atoms,

[0138] E₃ is alkyl of 8 to 18 carbon atom, aryl of 6 to 10 carbon atomsor said aryl substituted one or two alkyl of 1 to 4 carbon atoms, and

[0139] with the proviso that E₁ is not phenylalkyl when G₂ is E₃SO— orE₃SO₂—.

[0140] Most preferably, in the compound of formula I′,

[0141] G₂ is cyano, E₃SO₂—, CF₃—, —CO—G₃ or —CO—N(G₃)₂,

[0142] G₃ is alkyl of 1 to 8 carbon atoms,

[0143] E₁ is hydrogen, phenyl or α-cumyl,

[0144] E₂ is alkyl of 4 to 12 carbon atoms, and

[0145] E₃ is phenyl or octyl, and with the proviso that E₁ is notα-cumyl when G₂ is E₃SO₂—.

[0146] Especially preferred are the compounds of formula I′ where G₂ isCF₃—, E₁ is α-cumyl, and E₂ is tert-butyl or tert-octyl.

[0147] The instant invention also pertains to a composition stabilizedagainst thermal, oxidative or light-induced degradation which comprises,

[0148] (a) an organic material subject to thermal, oxidative orlight-induced degradation, and

[0149] (b) an effective stabilizing amount of a compound of formula I,II, III or IV.

[0150] Preferably, the organic material is a natural, semi-synthetic orsynthetic polymer, especially a thermoplastic polymer.

[0151] Most preferably, the polymer is a polyolefin or polycarbonate,especially polyethylene or polypropylene; most especially polypropylene.

[0152] In another preferred embodiment of the instant invention, theorganic material is a resin selected from the group consisting of athermoset acrylic melamine resin, an acrylic urethane resin, an epoxycarboxy resin, a silane modified acrylic melamine, an acrylic resin withcarbamate pendant groups crosslinked with melamine or an acrylic polyolresin crosslinked with melamine containing carbamate groups.

[0153] Most preferably, the resin is a thermoset acrylic melamine resinor an acrylic urethane resin.

[0154] In yet another preferred embodiment of the instant invention, theorganic material is a recording material.

[0155] The recording materials according to the invention are suitablefor pressure-sensitive copying systems, photocopying systems usingmicrocapsules, heat-sensitive copying systems, photographic materialsand ink jet printing.

[0156] The recording materials according to the invention aredistinguished by an unexpected improvement in quality, especially withregard to the fastness to light.

[0157] The recording materials according to the invention have theconstruction known for the particular use. They consist of a customarycarrier, for example, paper or plastic film, which has been coated withone or more layers. Depending on the type of material, these layerscontain the appropriate necessary components, in the case ofphotographic materials, for example, silver halide emulsions, dyecouplers, dyes and the like. Material particularly suitable for ink jetprinting has a layer particularly absorptive for ink on a customarycarrier. Uncoated paper can also be employed for ink jet printing. Inthis case the paper acts at the same time as the carrier material and asthe ink-absorbent layer. Suitable material for ink jet printing is, forexample, described in U.S. Pat. No. 5,073,448 which is incorporatedherein by reference.

[0158] The recording material can also be transparent as, for example,in the case of projection films.

[0159] The compounds of formula I, II, III or IV can be incorporatedinto the carder material as early as the production of the latter, inthe production of paper, for example, being added to the paper pulp. Asecond method of application is to spray the carder material with anaqueous solution of compounds of formula I, II, III or IV or to add thecompounds to the coating composition.

[0160] Coating compositions intended for transparent recording materialssuitable for projection cannot contain any particles which scatterlight, such as pigments and fillers.

[0161] The dye-binding coating composition can contain a number of otheradditives, for example, antioxidants, light stabilizers (including alsoUV absorbers which do not fall under the scope of the UV absorbers ofthis invention), viscosity improvers, fluorescent brighteners, biocidesand/or antistatic agents.

[0162] The coating composition is usually prepared as follows: thewater-soluble components, for example, the binder, are dissolved inwater and stirred together; the solid components, for example, fillersand other additives already described, are dispersed in this aqueousmedium; and disperison is advantageously carried out by means ofdevices, for example, ultrasonic systems, turbine stirrers,homogenizers, colloid mills, bead mills, sand mills, high-speed stirrersand the like. The compounds of formula I, II, III or IV can be easilyincorporated into the coating composition.

[0163] The recording material according to this invention preferablycontains 1 to 5000 mg/m², in particular 50-1200 mg/m², of a compound offormula I.

[0164] As already mentioned, the recording materials according to theinvention embrace a wide field. The compounds of formula I, II, III orIV can, for example, be employed in pressure-sensitive copying systems.They can be introduced either into the paper in order to protect themicroencapsulated dye precursors there from light, or into the binder ofthe developer layer in order to protect the dyes formed there.

[0165] Photocopying systems using light-sensitive microcapsules whichare developed by means of pressure are described in U.S. Pat. Nos.4,416,966; 4,483,912; 4,352,200; 4,535,050; 4,535,463; 4,551,407;4,562,137 and 4,608,330; and also in EP-A 139,479; EP-A 162,664; EP-A164,931; EP-A 237,024; EP-A 237,025 and EP-A 260,129. In all thesesystems, the compounds can be put into the dye-receiving layer. Thecompounds can, however, also be put into the donor layer in order toprotect the color formers from light.

[0166] Photographic materials which can be stabilized are photographicdyes and layers containing such dyes or precursors thereof, for example,photographic paper and films. Suitable materials are, for example,described in U.S. Pat. No. 5,364,749 which is incorporated herein byreference. The compounds of formula I, II, III or IV act here as a UVfilter against electrostatic flashes. In color photographic materials,couplers and dyes are also protected against photochemicaldecomposition.

[0167] The instant compounds can be used for all types of colorphotographic materials. For example, they can be employed for colorpaper, color reversal paper, direct-positive color material, colornegative film, color positive film, color reversal film and the like.They are preferably used inter alia for photographic color materialwhich contains a reversal substrate or form positives.

[0168] Color-photographic recording materials usually contain, on asupport, a blue-sensitive and/or a green-sensitive and/or ared-sensitive silver halide emulsion layer and, if desired, a protectionlayer, with the instant compounds being, preferably, either in thegreen-sensitive or the red-sensitive layer or in a layer between thegreen-sensitive and the red-sensitive layer or in a layer on top of thesilver halide emulsion layers.

[0169] The compounds of formula I, II, III or IV can also be employed inrecording materials based on the principles of photopolymerization,photoplasticization or the rupture of microcapsules, or in cases whereheat-sensitive and light-sensitive diazonium salts, leuko dyes having anoxidizing agent or dye lactones having Lewis acids are used.

[0170] Furthermore, the instant compounds can be employed in recordingmaterials for dye diffusion transfer printing, thermal wax transferprinting and non-matrix printing and for use with electrostatic,electrographic, electrophoretic, magnetographic andlaser-electrophotographic printers and pen-plotters. Of the above,recording materials for dye diffusion transfer printing are preferred,for example, as described in EP-A 507,734.

[0171] The instant compounds can also be employed in inks, preferablyfor ink jet printing, for example, as described in U.S. Pat. No.5,098,477 which is incorporated herein by reference.

[0172] The compounds of this invention exhibit superior hydrolyticstability, handling and storage stability as well as good resistance toextractability when present in a stabilized composition.

[0173] The methodology to make the instant compounds is described in theprior art. The intermediates needed to make the instant compounds arelargely items of commerce.

[0174] Preferred compounds are those in which one of X and Y is —O—; andparticularly those in which both X and Y are —O—.

[0175] In general polymers which can be stabilized include

[0176] 1. Polymers of monoolefins and diolefins, for examplepolypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyisoprene or polybutadiene, as well as polymers of cycloolefins, forinstance of cyclopentene or norbornene, polyethylene (which optionallycan be crosslinked), for example high density polyethylene (HDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),branched low density polyethylene (BLDPE).

[0177] Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

[0178] a) radical polymerisation (normally under high pressure and atelevated temperature).

[0179] b) catalytic polymerisation using a catalyst that normallycontains one or more than one metal of groups IVb, Vb, VIb or VIII ofthe Periodic Table. These metals usually have one or more than oneligand, typically oxides, halides, alcoholates, esters, ethers, amines,alkyls, alkenyls and/or aryls that may be either π- or σ-coordinated.These metal complexes may be in the free form or fixed on substrates,typically on activated magnesium chloride, titanium(III) chloride,alumina or silicon oxide. These catalysts may be soluble or insoluble inthe polymerisation medium. The catalysts can be used by themselves inthe polymerisation or further activators may be used, typically metalalkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metalalkyloxanes, said metals being elements of groups Ia, Ia and/or IIIa ofthe Periodic Table. The activators may be modified conveniently withfurther ester, ether, amine or silyl ether groups. These catalystsystems are usually termed Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0180] 2. Mixtures of the polymers mentioned under 1), for examplemixtures of polypropylene with polyisobutylene, polypropylene withpolyethylene (for example PP/HDPE, PP/LDPE) and mixtures of differenttypes of polyethylene (for example LDPE/HDPE).

[0181] 3. Copolymers of monoolefins and diolefins with each other orwith other vinyl monomers, for example ethylene/propylene copolymers,linear low density polyethylene (LLDPE) and mixtures thereof with lowdensity polyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

[0182] 4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

[0183] 5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

[0184] 6. Copolymers of styrene or α-methylstyrene with dienes oracrylic derivatives, for example styrene/butadiene,styrene/acrylonitrile, styrene/alkyl methacrylate,styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate,styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength of styrene copolymers and anotherpolymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer, and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

[0185] 7. Graft copolymers of styrene or α-methylstyrene, for examplestyrene on polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

[0186] 8. Halogen-containing polymers such as polychloroprene,chlorinated rubbers, chlorinated or sulfochlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epi-chlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

[0187] 9. Polymers derived from α,β-unsaturated acids and derivativesthereof such as polyacrylates and polymethacrylates; polymethylmethacrylates, polyacrylamides and polyacrylonitriles, impact-modifiedwith butyl acrylate.

[0188] 10. Copolymers of the monomers mentioned under 9) with each otheror with other unsaturated monomers, for example acrylonitrile/ butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.

[0189] 11. Polymers derived from unsaturated alcohols and amines or theacyl derivatives or acetals thereof, for example polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine;as well as their copolymers with olefins mentioned in 1) above.

[0190] 12. Homopolymers and copolymers of cyclic ethers such aspolyalkylene glycols, polyethylene oxide, polypropylene oxide orcopolymers thereof with bisglycidyl ethers.

[0191] 13. Polyacetals such as polyoxymethylene and thosepolyoxymethylenes which contain ethylene oxide as a comonomer;polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

[0192] 14. Polyphenylene oxides and sulfides, and mixtures ofpolyphenylene oxides with styrene polymers or polyamides.

[0193] 15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

[0194] 16. Polyamides and copolyamides derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, for example polyamide 4, polyamide 6, polyamide6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromaticpolyamides starting from m-xylene diamine and adipic acid; polyamidesprepared from hexamethylenediamine and isophthalic or/and terephthalicacid and with or without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

[0195] 17. Polyureas, polyimides, polyamide-imides andpolybenzimidazoles.

[0196] 18. Polyesters derived from dicarboxylic acids and diols and/orfrom hydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

[0197] 19.- Polycarbonates and polyester carbonates.

[0198] 20. Polysulfones, polyether sulfones and polyether ketones.

[0199] 21. Crosslinked polymers derived from aldehydes on the one handand phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

[0200] 22. Drying and non-drying alkyd resins.

[0201] 23. Unsaturated polyester resins derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

[0202] 24. Crosslinkable acrylic resins derived from substitutedacrylates, for example epoxy acrylates, urethane acrylates or polyesteracrylates.

[0203] 25. Alkyd resins, polyester resins and acrylate resinscrosslinked with melamine resins, urea resins, polyisocyanates or epoxyresins.

[0204] 26. Crosslinked epoxy resins derived from polyepoxides, forexample from bisglycidyl ethers or from cycloaliphatic diepoxides.

[0205] 27. Natural polymers such as cellulose, rubber, gelatin andchemically modified homologous derivatives thereof, for examplecellulose acetates, cellulose propionates and cellulose butyrates, orthe cellulose ethers such as methyl cellulose; as well as rosins andtheir derivatives.

[0206] 28. Blends of the aforementioned polymers (polyblends), forexample PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.

[0207] 29. Naturally occurring and synthetic organic materials which arepure monomeric compounds or mixtures of such compounds, for examplemineral oils, animal and vegetable fats, oil and waxes, or oils, fatsand waxes based on synthetic esters (e.g. phthalates, adipates,phosphates or trimellitates) and also mixtures of synthetic esters withmineral oils in any weight ratios, typically those used as spinningcompositions, as well as aqueous emulsions of such materials.

[0208] 30. Aqueous emulsions of natural or synthetic rubber, e.g.natural latex or latices of carboxylated styrene/butadiene copolymers.

[0209] 31. Polysiloxanes such as the soft, hydrophilic polysiloxanesdescribed, for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

[0210] 32. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

[0211] 33. Radiation curable compositions containing ethylenicallyunsaturated monomers or oligomers and a polyunsaturated aliphaticoligomer.

[0212] 34. Epoxymelamine resins such as light-stable epoxy resinscrosslinked by an epoxy functional coetherified high solids melamineresin such as LSE-4103 (Monsanto).

[0213] In general, the compounds of the present invention are employedin from about 0.01 to about 5% by weight of the stabilized composition,although this will vary with the particular substrate and application.An advantageous range is from about 0.05 to about 3%, and especially0.05 to about 1%.

[0214] The stabilizers of the instant invention may readily beincorporated into the organic polymers by conventional techniques, atany convenient stage prior to the manufacture of shaped articlestherefrom. For example, the stabilizer may be mixed with the polymer indry powder form, or a suspension or emulsion of the stabilizer may bemixed with a solution, suspension, or emulsion of the polymer. Theresulting stabilized polymer compositions of the invention mayoptionally also contain from about 0.01 to about 5%, preferably fromabout 0.025 to about 2%, and especially from about 0.1 to about 1% byweight of various conventional additives, such as the materials listedbelow, or mixtures thereof.

[0215] 1. Antioxidants

[0216] 1.1. Alkylated monophenols, for example,

[0217]

[0218] 2,6-di-tert-butyl-4-methylphenol

[0219] 2-tert-butyl-4,6-dimethylphenol

[0220] 2,6-di-tert-butyl-4-ethylphenol

[0221] 2,6-di-tert-butyl-4-n-butylphenol

[0222] 2,6-di-tert-butyl-4-i-butylphenol

[0223] 2,6-di-cyclopentyl-4-methylphenol

[0224] 2-(α-methylcyclohexyl)-4,6-dimethylphenol

[0225] 2,6-di-octadecyl-4-methylphenol

[0226] 2,4,6-tri-cyclohexylphenol

[0227] 2,6-di-tert-butyl-4-methoxymethylphenol

[0228]

[0229] 1.2. Alkylated hydroquinones, for example,

[0230]

[0231] 2,6-di-tert-butyl-4-methoxyphenol

[0232] 2,5-di-tert-butyl-hydroquinone

[0233] 2,5-di-tert-amyl-hydroquinone

[0234] 2,6-diphenyl-4-octadecyloxyphenol

[0235]

[0236] 1.3. Hydroxylated thiodiphenyl ethers, for example,

[0237]

[0238] 2,2′-thio-bis-(6-tert-butyl-4-methylphenol)

[0239] 2,2′-thio-bis-(4-octylphenol)

[0240] 4,4′-thio-bis-(6-tert-butyl-3-methylphenol)

[0241] 4,4′thio-bis-(6-tert-butyl-2-methylphenol)

[0242]

[0243] 1.4. Alkylidene-bisphenols, for example,

[0244]

[0245] 2,2′-methylene-bis-(6-tert-butyl-4-methylphenol)

[0246] 2,2′-methylene-bis-(6-tert-butyl-4-ethylphenol)

[0247] 2,2′-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

[0248] 2,2′-methylene-bis-(4-methyl-6-cyclohexylphenol)

[0249] 2,2′-methylene-bis-(6-nonyl-4-methylphenol)

[0250] 2,2′-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

[0251] 2,2′-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

[0252] 2,2′-methylene-bis-(4,6-di-tert-butylphenol)

[0253] 2,2′-ethylidene-bis-(4,6-di-tert-butylphenol)

[0254] 2,2′-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

[0255] 4,4′-methylene-bis-(2,6-di-tert-butylphenol)

[0256] 4,4′-methylene-bis-(6-tert-butyl-2-methylphenol)

[0257] 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

[0258] 2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

[0259] 1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

[0260]1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane

[0261] ethyleneglycolbis-[3,3-bis-(3′-tert-butyl-4′-hydroxyphenyl)-butyrate]

[0262] di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

[0263]di-[2-(3′-tert-butyl-2′-hydroxy-5′-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

[0264]

[0265] 1.5. Benzyl compounds, for example,

[0266]

[0267]1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

[0268] di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide

[0269] 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctylester

[0270] bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiolterephthalate

[0271] 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate

[0272] 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate

[0273] 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecylester

[0274] 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethylester, calcium-salt

[0275]

[0276] 1.6. Acylaminophenols, for example,

[0277]

[0278] 4-hydroxy-lauric acid anilide

[0279] 4-hydroxy-stearic acid anilide

[0280]2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

[0281] octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

[0282]

[0283] 1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionicacid with monohydric or polyhydric alcohols, for example, methanoldiethylene glycol octadecanol triethylene glycol 1,6-hexanediolpentaerythritol neopentyl glycol tris-hydroxyethyl isocyanuratethiodiethylene glycol di-hydroxyethyl oxalic acid diamidetriethanolamine triisopropanolamine

[0284] 1.8. Esters ofβ-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydricor polyhydric alcohols, for example, methanol diethylene glycoloctadecanol triethylene glycol 1,6-hexanediol pentaerythritol neopentylglycol tris-hydroxyethyl isocyanurate thiodiethylene glycoldi-hydroxyethyl oxalic acid diamide triethanolamine triisopropanolamine

[0285] 1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionicacid for example,

[0286]

[0287] N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

[0288]N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

[0289] N,N-′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

[0290]

[0291] 1.10 Diarylamines, for example,

[0292] diphenylamine, N-phenyl-1-naphthylamine,N-(4-tert-octylphenyl)-1-naphthylamine,4,4′-di-tert-octyl-diphenylamine, reaction product ofN-phenylbenzylamine and 2,4,4-trimethylpentene, reaction product ofdiphenylamine and 2,4,4-trimethylpentene, reaction product ofN-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.

[0293]

[0294] 2. UV absorbers and light stabilizers

[0295]

[0296] 2.1. 2-(2′-Hydroxyphenyl)-benzotriazoles, for example, the5′-methyl-, 3′,5′-di-tert-butyl-, 5′-tert-butyl-,5′-(1,1,3,3-tetramethylbutyl)-5-chloro-3′,5′-di-tert-butyl-,5-chloro-3′-tert-butyl-5′-methyl-, 3′-sec-butyl-5′-tert-butyl-,4′-octoxy, 3′,5′-di-tert-amyl-, 3′,5′-bis-(α,α-dimethylbenzyl),3′-tert-butyl-5′-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,3′-dodecyl-5′-methyl-, and 3′-tert-butyl-5′-(2-octyloxycarbonyl)ethyl-,and dodecylated-5′-methyl derivatives.

[0297] 2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-,4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy,4,2′,4′-trihydroxy- and 2′-hydroxy-4,4′-dimethoxy derivatives.

[0298] 2.3. Esters of optionally substituted benzoic acids for example,phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

[0299] 2.4. Acrylates, for example, (α-cyano-β,β-diphenylacrylic acidethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methylester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butylester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-5-cyanovinyl)-2-methyl-indoline.

[0300] 2.5. Nickel compounds, for example, nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

[0301] 2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N′-(2,2,6,6-tetra-methylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1′(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

[0302] 2.7. Oxalic acid diamides, for example,4,4′-di-octyloxy-oxanilide,2,2′-di-octyloxy-5,5′-di-tert-butyl-oxanilide,2,2′-di-dodecyloxy-5,5′-di-tert-butyl-oxanilide,2-ethoxy-2′-ethyl-oxanilide, N,N′-bis (3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

[0303] 2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)-phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chloro-phenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

[0304] 3. Metal deactivators, for example, N,N′-diphenyloxalic aciddiamide, N-salicylal-N′-salicyloyl-hydrazine,N,N′-bis-salicyloylhydrazine,N,N′-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

[0305] 4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecyl-pentaerythritol diphosphite,di-(2,4,6-tri-tert-butylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4′-diphenylylenediphosphonite.

[0306] 5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

[0307] 6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecyl-hydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

[0308] 7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

[0309] 8. Polyamide stabilizers, for example copper salts in combinationwith iodides and/or phosphorus compounds and salts of divalentmanganese.

[0310] 9. Basic co-stabilizers, for example, melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali metal salts and alkaline earth metal salts of higher fatty acidsfor example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and Kpalmitate, antimony pyrocatecholate or zinc pyrocatecholate.

[0311] 10. Nucleating agents, for example, 4-tert-butyl-benzoic acid,adipic acid, diphenylacetic acid.

[0312] 11. Fillers and reinforcing agents, for example, calciumcarbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, bariumsulfate, metal oxides and hydroxides, carbon black, graphite.

[0313] 12. Other additives, for example, plasticizers, lubricants,emulsifiers, pigments, optical brighteners, flameproofing agents,anti-static agents, blowing agents and thiosynergists such as dilaurylthiodipropionate or distearyl thiodipropionate.

[0314] 13. Benzofuranones and indolinones, for example those disclosedin U.S. Pat. No. 4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No.5,175,312, or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzo-furan-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)-benzofuran- 2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-di-methyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

[0315] The co-stabilizers, with the exception of the benzofuranoneslisted under 11, are added for example in concentrations of 0.01 to 10%,relative to the total weight of the material to be stabilized.

[0316] Further preferred compositions comprise, in addition tocomponents (a) and (b) further additives, in particular phenolicantioxidants, light stabilizers or processing stabilizers.

[0317] Particularly preferred additives are phenolic antioxidants (itemI of the list), sterically hindered amines (item 2.6 of the list),phosphites and phosphonites (item 4 of the list) and peroxide-destroyingcompounds (item 5.) of the list.

[0318] Additional additives (stabilizers) which are also particularlypreferred are benzofuran-2-ones, such as described, for example, in U.S.Pat. No. 4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312.

[0319] The phenolic antioxidant of particular interest is selected fromthe group consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol,2,2′-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, and N,N ′-bis[2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

[0320] A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-tri-methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2′-ethylidene-bis(4,6-di-tert-butylphenol).

[0321] The hindered amine compound of particular interest is selectedfrom the group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane,polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazineand 4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4′-hexamethylenebis-(amino-2,2,6,6-tetra-methylpiperidine) and1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensation product of2,4-dichloro-6-morpholino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N′″-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,mixed[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, octamethylenebis(2,2,6,6-tetramethyl-piperidin-4-carboxylate),4,4′-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one),N-2,2,6,6-tetramethyl-piperidin-4-yl-n-dodecylsuccinimide,N-1,2,2,6,6-pentamethyl-piperidin-4-yl-n-dodecylsuccinimide,N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide,1-acetyl3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetra-methylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino], and2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.

[0322] A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N′″-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane.di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],or2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.

[0323] The instant composition can additionally contain another UVabsorber selected from the group consisting of the s-triazines, theoxanilides, the hydroxybenzophenones, benzoates and theα-cyanoacrylates.

[0324] Particularly, the instant composition may additionally contain aneffective stabilizing amount of at least one other2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; orhindered amine or mixtures thereof.

[0325] Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected fromthe group consisting of

[0326]

[0327] 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

[0328] 2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;

[0329]2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-octylphenyl]-2H-benzotriazole;

[0330]2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole;and

[0331]2-{(2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzo-triazole.

[0332] Preferably, the other tris-aryl-s-triazine is selected from thegroup consisting of

[0333]

[0334]2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;

[0335] 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;

[0336]2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-phenyl]-s-triazine;and

[0337] 2-(2-hydroxyethylamino)-4,6-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)amino]-s-triazine.

[0338] The alkyd resin lacquers which can be stabilized against theaction of light and moisture in accordance with the instant inventionare the conventional stoving lacquers which are used in particular forcoating automobiles (automobile finishing lacquers), for examplelacquers based on alkyd/melamine resins and alkyd/acrylic/melamineresins (see H. Wagner and H. F. Sarx, “Lackkunstharze” (1977), pages99-123). Other crosslinking agents include glycouril resins, blockedisocyanates or epoxy resins.

[0339] The lacquers stabilized in accordance with the invention aresuitable both for metal finish coatings and solid shade finishes,especially in the case of retouching finishes, as well as various coilcoating applications. The lacquers stabilized in accordance with theinvention are preferably applied in the conventional manner by twomethods, either by the single-coat method or by the two-coat method. Inthe latter method, the pigment-containing base coat is applied first andthen a covering coat of clear lacquer over it.

[0340] It is also to be noted that the compounds of the presentinvention are applicable for use in non-acid catalyzed thermoset resinssuch as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyesterresins, optionally modified with silicon, isocyanates or iso-cyanurates.The epoxy and epoxy-polyester resins are crosslinked with conventionalcross-linkers such as acids, acid anhydrides, amines and the like.Correspondingly, the epoxide may be utilized as the crosslinking agentfor various acrylic or polyester resin systems that have been modifiedby the presence of reactive groups on the backbone structure.

[0341] When used in two-coat finishes, the compounds of the instantinvention can be incorporated in the clear coat or both in the clearcoat and in the pigmented base coat.

[0342] When water-soluble, water miscible or water dispersible coatingare desired ammonium salts of acid groups present in the resin areformed. Powder coating composition can be prepared by reacting glycidylmethacrylate with selected alcohol components.

[0343] The instant benzotriazoles are made by conventional methods forpreparing such compounds. The usual procedure involves the diazotizationof a substituted o-nitroaniline followed by coupling the resultantdiazonium salt with a substituted phenol and reduction of the azobenzeneintermediate to the corresponding desired benzotriazole. The startingmaterials for these benzotriazoles are largely items of commerce or canbe prepared by normal methods of organic synthesis.

[0344] While the instant benzotriazoles with their enhanced durabilityare particularly suited for automotive coating applications, it iscontemplated that they will also be espeically useful in otherapplications where their enhanced durability is required such as insolar films and the like.

[0345] The following examples are for illustrative purposes only and arenot to be construed to limit the scope of the instant invention in anymanner whatsoever.

EXAMPLE 15-Trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0346] a. Diazotization of 4-amino-3-nitro-benzotrifluoride

[0347] To a 500 ml 3-necked flask, equipped with a mechanical stirrer,are added 41.2 g of 4-amino-3-nitro-benzotrifluoride, 52 ml ofconcentrated hydrochloride acid and 100 ml of distilled water. Thestirred solution is cooled to 5° C. and 17.3 g of sodium nitritedissolved in 50 ml of water are added. The solution is stirred at 0 to5° C. for two hours, then filtered and stored at −10° C.

[0348] b. Monoazo adduct

[0349] To a 1000 ml flask, fitted with a mechanical stirrer, are added40 g of sodium hydroxide dissolved in 200 ml of methanol and 32.4 g of2-α-cumyl-4-tert-octylphenol in 50 ml of xylene. The solution is cooledto 5° C. and the diazo solution of 4-amino-nitro-benzotrifluorideprepared in part a. is added at 0 to 5° C. over a two-hour period. Then100 ml of xylene are added and the organic layer is washed with water,aqueous hydrochloride acid, water, aqueous sodium bicarbonate solutionand finally water. The solvent is removed under reduced pressure and theresidue is purified by chromatography (silica gel, heptane:ethyl acetate95:5) to yield 42.1 g of the adduct product as a dark red paste.

[0350] c. Reduction of the monoazo adduct

[0351] A 1000 ml flask is charged with 20 g of sodium hydroxide, 40 mlof water, 42.1 g of the monoazo adduct prepared in part b. and 400 ml ofethanol. The mixture is warmed to 80° C. and 27 g of formamidinesulfinic acid is added in portions with stirring. After 1.5 hours, thesolution is cooled to room temperature and 100 ml of water are added.The pH is adjusted to pH 7 with concentrated hydrochloric acid. Theethanol is removed under vacuum and the water layer is extracted withmethylene chloride. The solvent is then evaporated in vacuo and theresidue is purified by chromatography (silica gel, heptane:tolunen 9:1)and crystallized from ethanol. The title compound is obtained in a yieldof 5.6 g as a pale yellow solid melting at 119-121° C.

EXAMPLE 25-Fluoro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0352] The title compound is prepared according to the general procedureof Example 1 using 31.2 g of 4-fluoro-2-nitroaniline. In part c of theprocedure, an additional 9 g of formamidine sulfinic acid is required tocomplete the reduction. Purification of the crude product on silica gel(heptane:toluene, 1:1) yields 4.5 g of the title compound as a off-whitesolid. Further purification by recrystallization fromacetonitrile:toluene provides 1.1 g of the title compound melting at93-96° C.

EXAMPLE 35-Chloro-2-(2-hydroxy-3-(α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0353] The general procedure of Example 1 parts a and b is followed toprepare the monoazo intermediate of making the title compound from 339.3g of 4-chloro-2-nitro-aniline. The crude product is purified byrecrystallization from methanol to yield 70.9 g of deep red monoazoadduct.

Reduction of the Monoazo Adduct

[0354] A mixture of 11.8 g of sodium hydroxide and 138 g of 2-butanol isheated to 95° C. A solution of 60.1 g of the above monoazo adduct and1.3 g of 2,3-dichloro-1,4-naphtho-quinone in 90 g of 2-butanol is addedover a 90 minute period with stirring. The reaction mixture is heated toremove the 2-butanone byproduct with additional 2-butanol added toreplace the distillate. The reaction mixture is cooled to 85° C., washedwith 2.5 N sulfuric acid and brine and then concentrated. The residue isrecrystallized from methanol:xylene to yield 45.6 g of the titlecompound as a light yellow solid melting at 104-105° C.

EXAMPLE 45-Phenylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0355] To a stirred mixture of 75 g of5-chloro-2-(2-hydroxy-3-(α-cumyl-5-tert-octyl-phenyl)-2H-benzotriazoleand 105 g of N-methylpyrrolidone heated at 90° C. is added first 44.3 gof 45% aqueous potassium hydroxide solution over a 15-minute period then20.4 g of thiophenol over another 15 minutes. The reaction mixture isthen heated at 170-175° C. for four hours with water being removed bydistillation. After cooling to 100° C., xylene and water are added andthe resultant mixture is made acidic with 15% aqueous hydrogen chloridesolution. The organic layer is separated and washed with water and thenconcentrated. The crude product residue is recrystallized from methanolto yield 82 g of the tide compound as a pale yellow solid melting at124-125° C.

EXAMPLE 55-Benzenesulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0356] A 1000 mL flask is charged with 75.2 g of5-phenylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,prepared in Example 4, 102 g of xylene, 0.9 g of sodium tungstatedihydrate and 18.4 g of formic acid. The mixture is heated to 50° C. Tothis stirred mixture is slowly added 36.3 g of 50% hydrogen peroxide sothat the temperature does not exceed 85° C. Additional xylene and waterare then added. The organic layer is separated, washed with aqueoussodium sulfite, then twice with water and concentrated. The crudeproduct residue is recrystallized from methanol to yield 75.2 g of thetitle compound as a light yellow solid melting at 170-171° C.

EXAMPLE 65-Nonylthio-2-(2-hydroxy-3-(α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0357] Using the procedure of Example 4 with 30 g of5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole and17.6 g of nonyl mercaptan, the title compound is prepared.

EXAMPLE 75-Nonylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0358] 5-Nonylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, prepared in Example 6, is oxidizedto the sulfone without purification of the thio intermediate using 8.7 gof formic acid, 0.7 g of sodium tungstate dihydrate and 17.6 g of 50%hydrogen peroxide to yield the title compound as a yellow resinexhibiting a molecular ion of m/e 631.

EXAMPLE 85-Chloro-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole

[0359] The general procedure of Example 1 parts a and b are used toprepare the monoazo intermediate for the title compound from4-chloro-2-nitroaniline and 2-phenyl-4-tert-octylphenol. The crudeproduct is purified by recystallization from methanol to yield a deepred monoazo adduct.

[0360] The title compound is prepared according to the reductionprocedure of Example 3 from 65 g of the monoazo adduct prepared above,19.9 g of sodium hydroxide and 2.4 g of 2,3-dichloro-1,4-naphthoquinone.The crude product is purified by chromatography on silica gel(hexane:ethyl acetate, 5:1) yielding a fraction which is predominantlythe title compound exhibiting a molecular ion of m/e 433.

EXAMPLE 95-Phenylthio-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole

[0361] The title compound is prepared according to the procedure ofExample 4 from 20 g of the compound of Example 8, 20.4 g of 45% aqueouspotassium hydroxide, 10.3 g of thiophenol and 100 g ofN-methylpyrrolidone. The title compound is an oil purified bychromatography on silica gel using toluene as eluent.

EXAMPLE 105-Benzenesulfonyl-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole

[0362] The title compound is prepared according to the procedure ofExample 5 from 20 g of the thio compound of Example 9, 6.4 g of formicacid, 15.0 g of 50% hydrogen peroxide and 0.6 g of sodium tungstatedihydrate. Recrystallization of 2.5 g of crude material fromxylene/methanol yields 2.0 g of the purified title compound as a lightyellow powder melting at 204-206° C.

EXAMPLE 11 Mixture of5-Chloro-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzotriazole (alkyl beingindependently C₄, C₈, C₁₂ and C₁₆)

[0363] A mixture of 65.4 g of5-chloro-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzo-triazole, 45 mL ofdodecene and 13 mL of methane sulfonic acid is heated to 170° C. undernitrogen. An additional 135 mL of dodecene is added over a 4.5 hourperiod. The reaction mixture is allowed to cool to 100° C. and thenquenched with 400 g of crushed ice and extracted thrice with ethylacetate. The organic layers are combined, washed with water, aqueoussodium bicarbonate, water again and brine, dried over anhydrousmagnesium sulfate and finally concentrated. The polymeric residue isremoved by bulb to bulb distillation under vacuum at 0.2 mm and up to210° C. Unreacted starting material is then removed by distillation (at0.01 mm, 160° C.) to give 45 g of the title mixture as a yellow oil.

EXAMPLE 12 Mixture of5-Phenylthio-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzotriazole (alkylbeing independently C₄, C₈, C₁₂ and C₁₆)

[0364] The title mixture is prepared according to the procedure ofExample 4 using 40 g the mixture of Example 11, 11.2 g of potassiumhydroxide and 12.3 mL of thiophenol.

EXAMPLE 13 Mixture of5-Benzenesulfonyl-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzotriazole(alkyl being independently C₄, C₈, C₁₂ and C₁₆)

[0365] A mixture of the crude product of Example 12, 350 mL ofisopropanol, 14.7 mL of formic acid and 1.8 mL of concentrated sulfuricacid are heated to reflux and 30 mL of 50% hydrogen peroxide is addeddropwise over a two-hour period. After an additional three hours atreflux, the reaction mixture is cooled and 10% aqueous sodium sulfiteand aqueous sodium bicarbonate are added. The isopropanol is evaporatedand the residue is extracted with methylene chloride. The organic layeris washed with water and then dried over anhydrous magnesium sulfate.The solution is concentrated to leave 45 g of crude product as a viscousprange oil. Some 30 g of this crude product is purified bychromatography on silica gel (heptane:ethyl acetate, 4:1) to yield 28.9g of the title mixture as a yellow oil.

EXAMPLE 145-Diphenylphosphinyl-2-(2-hydroxy-3,5-tert-butylphenyl)-2H-benzotriazole

[0366] To a flame-dried 500 mL three-necked round-bottomed flaskequipped with a condenser, magnetic stirrer and thermometer are charged100 mL of dimethyl sulfoxide, 7.41 g (0.066 mol) of potassiumtert-butoxide and 11.17 g (0.060 mol) of diphenyl-phosphine via asyringe. A slurry of 10.56 g (0.030 mol) of5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole in 50 mLof dimethyl sulfoxide is added all at once to the red mixture. Theresultant brown solution is stirred at 135° C. for 3.5 hours and thencooled to room temperature. The mixture is quenched with a portion ofsaturated ammonium chloride solution and ethyl acetate is then added.The organic layer is separated and washed thrice with water, once withbrine and then dried over anhydrous magnesium sulfate. To the solutionis added 50% hydrogen peroxide resulting in an exotherm. The mixture isallowed to sit for 30 minutes, then washed once with 10% sodiummetabisulfite solution thrice with saturated sodium bicarbonate solutiononce with brine and finally dried over anhydrous magnesium sulfate. Themixture is filtered with a plug of silica gel and the solvent is removedunder reduced pressure to yield 8.0 g of a crude yellow solid. The crudeproduct is treated with medium pressure chromatography usingheptane:ethyl acetate, 1:1 to afford 4.2 g (27% yield) of the titlecompound as a yellow solid melting at 98-100° C.

EXAMPLE 155-Diphenylphosphinyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0367] Following the procedure of Example 14, the title compound isprepared when5-chloro-2-(2-hydroxy-3-(α-cumyl-5-tert-octylphenyl)-2H-benzotriazole isused as the starting benzotriazole intermediate.

EXAMPLES 16-26

[0368] Following the general procedure of Example 1, the followingadditional 2H-benzotriazoles of formula I′ are prepared. Example G₂ E₁E₂ 16 CF₃ phenyl tert-octyl 17 CF₃ α-cumyl tert-butyl 18 CN α-cumyltert-octyl 19 CN α-cumyl nonyl 20 CN α-cumyl tert-butyl 21 COOCH₃α-cumyl dodecyl 22 F phenyl tert-octyl 23 CF₃ α-cumyl nonyl 24 CF₃α-cumyl dodecyl 25 CON(Bu)₂ α-cumyl tert-octyl 26 COOCH₃ phenyltert-octyl

EXAMPLE 275-Octylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0369] Using the procedure of Example 6 with5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole andoctyl mercaptan, the title compound is prepared.

EXAMPLE 285-Octylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0370]5-Octylthio-2-(2-hydroxy-3-(α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,prepared in Example 27, is oxidized to the sulfone without purificationof the thio intermediate using the general method of Example 7.

EXAMPLE 29 5-Chloro-2-(2,4-dihydroxyphenyl)-2H-benzotriazole

[0371] Following the general procedure of Example 1, parts a & b, themonoazo intermediate of the title compound is prepared from 17.3 g of4-chloro-2-nitroaniline to yield 34.7 g of a deep red monoazo adductwetcake.

Reduction of the Monoazo Adduct

[0372] A mixture of 20 g of sodium hydroxide, 500 mL of water and 26.3of the monoazo adduct wetcake prepared above is heated to 30° C. Zincpowder (33.0 g) is added incrementally over two hours. At the end ofthis addition, 180 g of 40% aqueous sodium hydroxide solution is addeddropwise over one hour. The mixture is stirred at ambient temperaturefor 96 hours. The zinc residue is removed by filtration. The aqueoussolution is neutralized to pH 5-6 and the resulting slurry is filtered.The resulting filter case is washed well with water and dried to yield22.5 g of crude product. The crude product is purified by Soxhletextraction with acetone to give 9.6 g of the title compound.

EXAMPLE 30 5-Chloro-2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole

[0373] A mixture of 6.5 g of5-chloro-2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 7.1 g of1-bromooctane, 5.2 g of anhydrous potassium carbonate and 100 mL ofacetone is refluxed for 24 hours. To the resulting mixture, about 100 mLof water and ethyl acetate are added, and 10.6 g of crude product isisolated. Column chromatography using petroleum ether yields 0.9 g ofthe title compound whose structure is confirmed by Hnmr and massspectrometry.

EXAMPLE 31 5-Trifluoromethyl-2-(2,4-dihydroxyphenyl)-2H-benzotriazole

[0374] Following the general procedure of Example 29, the title compoundis prepared from 10.3 g of 4-amino-3-nitrobenzotrifluoride to give 6.4 gof the title compound whose structure is confirmed by Hnmr.

EXAMPLE 325-Trifluoromethyl-2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole

[0375] The title compound is prepared following the general procedure ofExample 30 from 5.6 g of5-trifluoromethyl-2-(2,4-dihydroxyphenyl)-2H-benzotriazole. The crudeproduct is purified by column chromatography to yield 1.1 g of the titlecompound as a white solid melting at 79-81° C. The structure isconfirmed by Hnmr and mass spectrometry.

EXAMPLE 335-Trifluoromethyl-2-[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-2H-benzotriazole

[0376] A mixture of 2.3 g of5-trifluoromethyl-2-(2,4-dihydroxyphenyl)-2H-benzotriazole prepared inExample 31, 1.3 mL of butyl glycidyl ether and 100 mg of ethyltriphenyl-phosphonium bromide in 50 mL of xylene is heated to refluxunder nitrogen for 14 hours. Water (25 mL) and 25 mL of ethyl acetateare added and 3 g of the crude product is isolated. Recrystallizationfrom heptane give 2.1 g of the title compound whose structure isconfirmed by nmr.

EXAMPLE 345-Trifluoromethyl-2-(2-hydroxy-4-aminophenyl)-2H-benzotriazole

[0377] The title compound is prepared following the general proceduresof Example 1 and Example 29 starting with4-amino-3-nitrobenzotrifluoride and 3-aminophenol. The structure of theproduct is confirmed by nmr.

EXAMPLE 355-Trifluoromethyl-2-[2-hydroxy-4-(2-ethylhexanoylamino)phenyl]-2H-benzotriazole

[0378] To a mixture of 4 g of5-trifluoromethyl-2-(2-hydroxy-4-aminophenyl)-2H-benzotriazole and 1.4 gof triethylamine in 75 mL of toluene is added dropwise a mixture of2-ethylhexanoyl chloride in 125 mL of toluene. The resulting mixture istreated with 100 mL of water and the crude product formed is purified bycolumn chromatography to give 1.9 g of the title compound melting at179-181° C. The structure is confirmed by nmr.

EXAMPLE 365-Carbomethoxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazolea. Esterification of 4-amino-3-nitrobenzoic Acid

[0379] To a 2 L 3-necked flask fitted with a mechanical stirrer areadded 700 mL of methanol, 20 g of xylene, 14 g concentrated sulfuricacid and 100 g of 4-amino-3-nitrobenzoic acid. The solution is heated toreflux for 33 hours. The mixture is cooled to 35° C. and neutralized topH 7.8. Water (1 L) is added, the solid collected and washed with 500 mlto give after drying overnight 100.9 g of methyl4-amino-3-nitrobenzoate.

b. Diazotization of methyl 4-amino-3-nitrobenzoate

[0380] To a 1 L 3-necked flask fitted with a mechanical stirrer is added177 g of 96% sulfuric acid and then slowly over 90 minutes 11 g ofsodium nitrite. The mixture is warmed to 30° C. to initiate thereaction. The temperature is kept below 70° C. The mixture is thencooled to 15° C. and 30 g of methyl 4-amino-3-nitrobenzoate is addedover two hours keeping the temperature between 15-20° C. The mixture iscooled to 0° C. and 200 g of ice is added to make the solution suitablefor the coupling reaction to form a monoazo compound.

c. Monoazo Adduct

[0381] To a 2 L 3-necked flask fitted with a mechanical stirrer andaddition funnel are added 52 g of 2-(α-cumyl-4-tert-octylphenol, 20 g ofwater, 315 g of methanol, 7 g of xylene and 150 g of sodium hydroxide.The mixture is cooled to −5° C. and the diazonium salt solution preparedis step b. is added over a two hour period with cooling to keep thetemperature below 3° C. After the diazonium salt solution is added, thepH is adjusted to 6.5-7.0. The mixture is poured into 500 mL of xyleneand washed thrice with 500 mL of water at 60° C. The xylene is removedby distillation to give 186 g of the monoazo adduct containing residualxylene.

d. Reduction of the Monoazo Adduct

[0382] To a 500 mL flask fitted with a mechanical stirrer is added the186 g of monoadduct prepared in step c., 125 g of 2-butanol and 1.7 g of2,3-dichloro-1,4-naphthoquinone. The mixture is heated to 90° C. and theresulting solution is then charged to the addition funnel on a separateflask. In said second flask are added 175 g of 2-butanol and 18.6 g ofsodium hydroxide, The flask is heated to 95° C. and the monoazo solutionis added over two hours while distilling off methyl ethyl ketone and2-butanol. 2-Butanol (100 g) is added and an azeotrope is distilled off.The mixture is then cooled and 300 g of xylene and 200 mL of water areadded. The pH is adjusted to 7-7.5 with 20% sulfuric acid. At 60° C.,the aqueous phase is separated and the organic phase washed twice with200 mL of water. The xylene is removed by distillation and the residueformed is crystallized from methanol to give 8.8 g of the title compoundmelting at 141-143° C.

EXAMPLE 375-[N,N-Di-n-butylcarbamoyl-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl]-2H-benzotriazolea. Saponification of5-Carbomethoxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0383] To a 250 mL 3-necked flask equipped with a mechanical stirrer,thermometer, condenser and nitrogen inlet is added 1.8 g of potassiumhydroxide and 40 mL of methanol. The mixture is warmed to 40° C. todissolve the potassium hydroxide. To this solution is added 2.7 g of5-carbomethoxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,prepared in Example 36, in 40 mL of methanol. The reaction mixture isrefluxed for six hours. The mixture is then cooled and acidified withhydrochloric acid. Ether and ethyl acetate are added, and the organiclayer is separated and dried over anhydrous sodium sulfate. After vacuumstripping of the solvent, 2.5 g of5-carboxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole isisolated.

b.5-Chlorocarbonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0384] The 2.5 g of5-carboxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzo-triazole,prepared in step a., are placed in a 250 mL flask equipped with astirrer, thermometer, reflux condenser, Dean-Stark trap and nitrogeninlet. Toluene (100 mL) is added and the mixture is reflux to remove anytraces of water. The mixture is then cooled and 0.76 g of oxalylchloride in 15 mL of toluene is added. The reaction mixture is heatedslowly to 60° C. and held at 60-65° C. for eight hours till all thehydrogen chloride is expelled to give the acid chloride title compound.

c.5-[N,N-Di-n-butylcarbamoyl-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl]-2H-benzotriazole

[0385] To a 500 mL flask equipped with a mechanical stirrer, dryingtube, thermometer and dropping funnel are added 0.8 g ofdi-n-butylamine, 6 mL of pyridine and 25 mL of toluene, The mixture iscooled to 0° C. and the acid chloride solution prepared in step b. isplaced in the dropping funnel and added to the reaction mixture over a30-minute period at −5° C. to −10° C. The reaction mixture is stirred atthat temperature for 1.5 hours and then held at ambient temperatureovernight. The mixture was filtered and then vacuum stripped to give 3.0g of crude solids. The solid product is chromatographed to provide 1.2 gof the title compound as a tan solid melting at 131-133° C. Thestructure is confirmed by nmr and mass spectrometry m/z 596.

EXAMPLE 385-Trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole

[0386] The title compound is prepared according to general procedure ofExample 1 the diazo compound of 4-amino-3-nitrobenzotrifluoride and4-tert-octylphenol, and which is purified by chromatography on silicagel. Recrystallization of the product from either heptane or methanolyields the title compound as a near white solid melting at 80-81° C.

EXAMPLE 39

[0387] To ascertain the effect on thermal durability and loss rate froma high solids thermoset acrylic coating of various 2H-benzotriazole UVabsorbers substituted by a variety of electron withdrawing and electrondonating groups, the following tests are carried out.

[0388] A high solids thermoset acrylic clear coat is prepared by mixingan experimental acrylic polyol resin and hexamethoxymethylmelamine(Resimene® 747, Monsanto) at a solids ratio of 60/40. The dodecylbenzenesulfonic acid catalyst (Nacure® 5225; King Industries) is added at 0.70%by weight. A flow aid Modaflow® (Monsanto) is added at 0.25% by weightto form a model acrylic melamine resin system.

[0389] The model clear coat is reduced with xylene to a viscosity of26-27 second using a Zahn #2 cup and applied via a conventional airspray at 50 psi (3.5 Kg/cm²) over a 1″33 3″ (2.54 cm×7.62 cm) quartzslide. Cure is achieved by baking the slide for 30 minutes at 260° F.(127° C.). The clear coat is stabilized with 1% by weight of a hinderedamine light stabilizer,bis-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (TINUVIN®123, Ciba-Geigy). The various test benzotriazole UV absorbers areincorporated at the 5 mmol % by weight in the clear coat. The filmthickness on the quartz slides range from 1.15 to 1.41 mils (0.029 to0.036 mm).

[0390] The films on the quartz slides are weathered according to thefollowing conditions in Xenon Arc Weather-Ometer with a controlledirradiance at 6500 W, using inner quartz and outer borosilicate S-typefilter. The irradiation cycle is as follows: 40 minutes of straightirradiation with no water spray, followed by 20 minutes of light plusfront spray, followed by 60 minutes of light irradiation and finally by60 minutes dart plus rear spray (condensation). The setting is at 0.55W/M² at 340 nm, 1.98 kJ/hour. In the light cycle the black paneltemperature is controlled at 70±2° C. The relative humidity in the lightcycle is in the range of 50-55% and in the dark cycle 100%. Theabsorbance of the long wavelength UV band as a function of Xenon arcweathering hours are recorded in the table below.

[0391] To follow the loss of UV absorbers from the clear coats, UVspectra are measured initially and after weathering at regular timeintervals. The UV spectrophotometer measures absorbance linearly up to5.5 absorbance units using a reference beam attenuation technique.

[0392] It is assumed that the degradation products from the UV absorberdo not contribute to the UV spectrum. This is tested by following theratio of absorbance of the band at about 300 nm and the band at about340 nm. The ratio does not change upon weathering the sample, Thissuggests that the UV spectrum of the weathered films correspond to theamount of UV absorber remaining in the film with very little if anycontribution to the spectrum by photo degradants.

[0393] The data in the table below are based on formula A after 1211hours of exposure of the clear coats containing the test benzotriazoleUV absorbers. Units Absorbance Compound Loss G₂ R₁ R₂* A 1.7982 hydrogen—PO(OEt)₂ tert-octyl B 1.6300 hydrogen nitro tert-octyl C 1.4863phenyl-S— tert-butyl group I D 1.4002 hydrogen hydrogen group II E1.1872 methoxy tert-butyl methyl F 0.5259 hydrogen tert-butyl group II G0.4527 hydrogen hydrogen α-cumyl H 0.4420 hydrogen tert-butyl group I I0.4299 hydrogen tert-octyl α-cumyl J 0.4134 hydrogen hydrogen tert-octylK 0.3777 hydrogen tert-octyl tert-octyl L 0.3712 hydrogen tert-butylCH₂CH₂CH₂OH M 0.3433 hydrogen α-cumyl group II N 0.3098 cyano tert-butyltert-butyl O 0.2689 phenyl-SO₂— tert-butyl group I P 0.2576 hydrogenα-cumyl α-cumyl Q 0.2492 hydrogen α-cumyl tert-octyl

[0394] Inspection of these data leads to some clear conclusions aboutthe photostability of 2H-benzotriazole UV absorbers and about the natureof the substitution which will affect that photostability.

[0395] Increased photostability occurs when R₁ is α-cumyl or phenyl andwhen G₂ is an electron withdrawing group such as phenyl-sulfonyl orcyano.

[0396] The nature of the R₂ group has less influence on thephotostability of the benzotriazole UV absorbers.

[0397] From these observations, then an idealized benzotriazole UVabsorber might theoretically be designed where G₂ is an electronwithdrawing group, R₁ is an effective bulky group, and R₂ is a thermallystable moiety. One such idealized compound might be a benzotriazolewhere G₂ is phenylsulfonyl, R₁ is α-cumyl and R₂ is tert-octyl. Thisbenzotriazole is generically claimed in U.S. Pat. No. 5,280,124. Thedata given in Example 30 below confirms this prediction and this“idealized” compound does indeed exhibit a very low loss rate well belowthe present state of the art.

EXAMPLE 40

[0398] Following the general procedure of Example 39, a number ofadditional benzotriazole test compounds are incorporated into a highsolids thermoset acrylic melamine resin at such concentrations between1.93 and 3% by weight to give equal molar concentrations of testbenzotriazole in equal film thickness, and sufficient to give a startingabsorbance of approximately 2.0 absorbance units.

[0399] The test discs are exposed in a Xenon-Arc Weather-Ometer at X180cycle (0.45 Watts/M²). The initial UV absorbance is measured followed bymeasurements at roughly 250 hour intervals for the first 2000 hours andevery 500 hours thereafter. Each clear coat also contains 1% by weightof a hindered amine light stabilizer,bis-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, as well.

[0400] The data in the table below are based on compounds of formula Aafter 1253 hours of exposure of the clear coats containing the testbenzotriazole UV absorbers. Units Absorbance Compound Loss G₂ R₁ R₂ R0.2424 hydrogen phenyl α-cumyl Q 0.2351 hydrogen α-cumyl tert-octyl S0.1271 CF₃ α-cumyl tert-octyl T 0.1827 phenyl-SO₂ tert-butyl tert-butyl

[0401] The data in the table below are based on compounds of formula Aafter 1489 hours of exposure of the clear coats containing the testbenzotriazole UV absorbers. Units Absorbance Compound Loss G₂ R₁ R₂ R0.3724 hydrogen phenyl α-cumyl Q 0.287  hydrogen α-cumyl tert-octyl S0.1547 CF₃ α-cumyl tert-octyl T 0.2654 phenyl-SO₂ tert-butyl tert-butyl

[0402] The data in the table below are based on compounds of formula Aafter 2521 hours of exposure of the clear coats containing the testbenzotriazole UV absorbers. Units Absorbance Compound Loss G₂ R₁ R₂ R0.4824 hydrogen phenyl α-cumyl Q 0.4054 hydrogen α-cumyl tert-octyl S0.2192 CF₃ α-cumyl tert-octyl T 0.3570 phenyl-SO₂ tert-butyl tert-butyl

[0403] It is clear from the three tables above that Compounds S andespecially T which have an electron withdrawing group at the 5-positionof the benzo ring are significantly more durable than benzotriazoleswhich do not have such a group on the benzo ring.

[0404] The data in the table below are based on compounds of formula Aafter 1264 hours of exposure of the clear coats containing the testbenzotriazole UV absorbers. Units Absorbance Compound Loss G₂ R₁ R₂ Q0.4054 hydrogen α-cumyl tert-octyl S 0.2192 CF₃ α-cumyl tert-octyl T0.3570 phenyl-SO₂ tert-butyl tert-butyl U 0.0944 phenyl-SO₂ α-cumyltert-octyl V 0.1719 chloro α-cumyl tert-octyl W 0.1655 fluoro α-cumyltert-octyl X 0.1796 hydrogen phenyl tert-octyl

[0405] The data in the table below are based on compounds of formula Aafter 1518 hours of exposure of the clear coats containing the testbenzotriazole UV absorbers. Units Absorbance Compound Loss G₂ R₁ R₂ Q0.2662 hydrogen α-cumyl tert-octyl S 0.1116 CF₃ α-cumyl tert-octyl T0.2423 phenyl-SO₂ tert-butyl tert-butyl U 0.1114 phenyl-SO₂ α-cumyltert-octyl V 0.1955 chloro α-cumyl tert-octyl W 0.1668 fluoro α-cumyltert-octyl X 0.2220 hydrogen phenyl tert-octyl

[0406] The data in these tables clearly show that benzotriazolessubstituted by an electron withdrawing group on the benzo ring,particularly a group such as trifluoromethyl or phenyl-sulfonyl, areespecially durable as measured by low loss rate absorbance values afterexposure to actinic radiation. Compounds S, U, V and W are especiallydurable and fit the profile proposed above. Indeed, the prediction thatCompound U would be particularly durable is borne out by the data above.Inspection of the data for compounds T and U shows the added beneficialeffect of having an effective bulky group such as α-cumyl at the R₁position compared to a mere alkyl moiety such as tert-butyl at thatposition.

What is claimed is:
 1. A coating composition, stabilized with abenzotriazole, which benzotriazole exhibits enhanced durability and alow loss rate when incorporated in said coating, which compositioncomprises (a) a resin selected from the group consisting of a thermosetacrylic melamine resin, an acrylic urethane resin, an epoxy carboxyresin, a silane modified acrylic melamine, an acrylic resin withcarbamate pendant groups crosslinked with melamine or an acrylic polyolresin crosslinked with melamine containing carbamate groups, and (b)0.01 to 5% by weight, based on resin solids, of a benzotriazole offormula A, B, C or D

wherein G₁, G₂ or T is an electron withdrawing radical, G₁ is hydrogenor halogen, G₂ is halogen, nitro, cyano, R₃SO—, R₃SO₂—, —COOG₃, CF₃—,—P(O)(C₆H₅)₂, —CO—G₃, —CO—NH—G₃, —CO—N(G₃)₂, —N(G₃)—CO—G₃,

G₃ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight of branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,phenyl, or said phenyl or said phenylalkyl substituted on the phenylring by 1 to 4 alkyl of 1 to 4 carbon atoms, R₁ is hydrogen, straight orbranched chain alkyl of 1 to 24 carbon atoms, straight of branched chainalkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or saidphenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4carbon atoms, R₂ is straight or branched alkyl chain of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,phenyl, or said phenyl or said phenylalkyl substituted on the phenylring by 1 to 3 alkyl of 1 to 4 carbon atoms; or R₂ is hydroxyl or —OR₄where R₄ is straight or branched chain alkyl of 1 to 24 carbon atoms; orsaid alkyl substituted by one or more —OH, —OCO—R₁₁, —OR₄, —NCO or —NH₂groups or mixtures thereof; or said alkyl or said alkenyl interrupted byone or more —O—, —NH— or —NR₄— groups or mixtures thereof and which canbe unsubstituted or substituted by one or more —OH, —OR₄ or —NH₂ groupsor mixtures thereof; or R₂ is —SR₃, —NHR₃ or —N(R₃)₂; or R₂ is(CH₂)_(m)—CO—X—(Z)_(p)—Y—R₁₅ wherein X is —O— or —N(R₁₆)—, Y is —O— or—N(R₁₇)—, Z is C₂-C₁₂-alkylene, C₄-C₁₂-alkylene interrupted by one tothree nitrogen atoms, oxygen atoms or a mixture thereof, or isC₃-C₁₂-alkylene, butenylene, butynylene, cyclohexylene or phenylene,each substituted by a hydroxyl group, m is zero, 1 or 2, p is 1, or p isalso zero when X and Y are —N(R₁₆)— and —N(R₁₇)—, respectively, R₁₅ is agroup —CO—C(R₁₈)═C(H)R₁₉ or, when Y is —N(R₁₇)—, forms together with R₁₇a group —CO—CH═CH—CO—, wherein R₁₈ is hydrogen or methyl, and R₁₉ ishydrogen, methyl or —CO—X—R₂₀, wherein R₂₀ is hydrogen, C₁-C₁₂-alkyl ora group of the formula.

wherein the symbols R₁, R₃, X, Z, m and p have the meanings definedabove, and R₁₆ and R₁₇ independently of one another are hydrogen,C₁-C₁₂-alkyl, C₃-C₁₂-alkyl interrupted by 1 to 3 oxygen atoms, or iscyclohexyl or C₇-C₁₅aralkyl, and R₁₆ together with R₁₇ in the case whereZ is ethylene, also forms ethylene, n is 1 or 2, when n is 1, R₅ is Cl,OR₆ or NR₇R₈, or R₅ is —PO(OR₁₂)₂, —OSi(R₁₁)₃ or —OCO—R₁₁, or straightor branched chain C₁-C₂₄alkyl which is interrupted by —O—, —S— or —NR₁₁and which can be unsubstituted or substituted by —OH or —OCO—R₁₁, C₅-C₁₂cycloalkyl which is unsubstituted or substituted by —OH, straight chainor branched C₂-C₁₈alkenyl which is unsubstituted or substituted by —OH,C₇-C₁₅aralkyl, —CH₂—CHOH—R₁₃ or glycidyl, R₆ is hydrogen, straight orbranched chain C₁-C₂₄alkyl which is unsubstituted or substituted by oneor more OH, OR₄ or NH₂ groups, or —OR₆ is —(OCH₂CH₂)_(w)OH or—(OCH₂CH₂)_(w)OR₂₁ where w is 1 to 12 and R₂₁ is alkyl of 1 to 12 carbonatoms, R₇ and R₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms, straight or branched chain C₃-C₁₈alkyl which is interrupted by—O—, —S— or —NR₁₁—, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl,or R₇ and R₈ together with the N atom are a pyrrolidine, piperidine,piperazine or morpholine ring, when n is 2, R₅ is one of divalentradicals —O—R₉—O— or —N(R₁₁)—R₁₀—N(R₁₁)—, R₉ is C₂-C₈alkylene,C₄-C₈alkenylene, C₄alkynylene, cyclohexylene, straight or branched chainC₄-C₁₀alkylene which is interrupted by —O— or by—CH₂—CHOH—CH₂—O—R₁₄—O—CH₂—CHOH—CH₂—, R₁₀ being straight or branchedchain C₂-C₁₂alkylene which may be interrupted by —O—, cyclohexylene, or

or R₁₀ and R₁₁ with the two nitrogen atoms form a piperazine ring, R₁₄is straight or branched chain C₂-C₈alkylene, straight or branched chainC₄-C₁₀alkylene which is interrupted by —O—, cycloalkylene, arylene or

where R₇ and R₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms or R₇ and R₈ together are alkylene of 4 to 6 carbon atoms,3-oxapentamethylene, 3-iminopentamethylene or3-methyliminopentamethylene, R₁₁ is hydrogen, straight or branched chainC₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, straight or branched chain C₃-C₈alkenyl,C₆-C₁₄aryl or C₇-C₁₅aralkyl, R₁₂ is straight or branched chainC₁-C₁₈alkyl, straight or branched chain C₃-C₁₈alkenyl, C₅-C₁₀cycloalkyl,C₆-C₁₆aryl or C₇-C₁₅aralkyl, R₁₃ is H, straight chain or branchedC₁-C₁₈alkyl which is substituted by —PO(OR₁₂)₂, phenyl which isunsubstituted or substituted by OH, C₇-C₁₅aralkyl or —CH₂OR₁₂, R₃ isalkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms,alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms orsaid aryl substituted by one or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms, L is alkylene of 1 to 12 carbon atoms, alkylidene of2 to 12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and Tis —SO—, —SO₂—, —SO—E—SO—, —SO₂—E—SO₂—, —CO—, —CO—E—CO—, —COO—E—OCO—,—CO—NG₃—E—NG₃—CO— or —NG₃—CO—E—CO—NG₃—, where E is alkylene of 2 to 12carbon atoms, cycloalkylene of 5 to 12 carbon atoms, or alkyleneinterrupted or terminated by cyclohexylene of 8 to 12 carbon atoms,which benzotriazole exhibits enhanced durability and low loss ratevalues when the coating is exposed to actinic radiation as witnessed bya loss of less than 0.22 absorbance units after exposure for 1200 hours,or less than 0.27 absorbance units after 1500 hours exposure, or lessthan 0.40 absorbance units after 2500 hours exposure in a Xenon-ArcWeather-Ometer.
 2. A composition according to claim 1 wherein component(b) is a compound of formula A′

wherein G₂ is fluoro, chloro, cyano, R₃SO₂—, CF₃—, —CO—G₃, —COO—G₃ or—CO—N(G₃)₂ G₃ is alkyl of 1 to 12 carbon atoms, R₁ is hydrogen, alkyl of1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon atoms orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 or 2alkyl groups of 1 to 4 carbon atoms, R₂ is alkyl of 1 to 12 carbonatoms, phenyl, phenylalkyl of 7 to 15 carbon atoms or —CH₂CH₂COOG₄ whereG₄ is hydrogen, alkyl of 1 to 24 carbon atoms or said alkyl substitutedby OH, interrupted by one to six —O— atoms or both substituted by OH andinterrupted by one to six —O— atoms, and R₃ is alkyl of 1 to 18 carbonatom, aryl of 6 to 10 carbon atoms or said aryl substituted one or twoalkyl of 1 to 4 carbon atoms.
 3. A composition according to claim 2where in the compound of formula A′ G₂ is fluoro, chloro, cyano, R₃SO₂—,CF₃—, —COO—G₃ or —CO—N(G₃)₂, G₃ is alkyl of 1 to 8 carbon atoms, R₁ ishydrogen, phenyl or α-cumyl, R₂ is alkyl of 4 to 12 carbon atoms orphenyl, and R₃ is phenyl or alkyl of 8 to 12 carbon atoms.
 4. Acomposition according to claim 3 wherein G₂ is phenyl-SO₂—, octyl-SO₂—,fluoro or CF₃—, R₁ is α-cumyl or phenyl, and R₂ is tert-butyl ortert-octyl.
 5. A composition according to claim 1 wherein component (a)is a resin which is a thermoset acrylic melamine resin or an acrylicurethane resin.
 6. A composition according to claim 1 which additionallycontains a stabilizing amount of a phenolic antioxidant selected fromthe group consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol,2,2′-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocyanurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, andN,N′-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.7. A composition according to claim 6 wherein the phenolic antioxidantis neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2′-ethylidene-bis(4,6-di-tert-butylphenol).
 8. A composition accordingto claim 1 which additionally contains an effective stabilizing amountof a hindered amine selected from the group consisting ofbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4′-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensation product of2,4-dichloro-6-morpholino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N′″-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,mixed[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, octamethylenebis(2,2,6,6-tetramethylpiperidin-4-carboxylate),4,4′-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one),N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide,N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide,1-acetyl3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino], and2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.9. A composition according to claim 8 wherein the hindered amine isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N′″-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-pentamethyl-piperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],or2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.10. A composition according to claim 1 which additionally containsanother UV absorber selected from the group consisting of thes-triazines, the oxanilides, the hydroxybenzophenones, benzoates and theα-cyanoacrylates.
 11. A composition according to claim 10 wherein thecomposition additionally contains an s-triazine which is2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-phenyl]-s-triazine; or 2-(2-hydroxyethylamino)-4,6-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-s-triazine.12. A compound of formula I, II, III or IV

wherein G₁ is hydrogen or halogen, G₂ is cyano, E₃SO—, E₃SO₂—, —COOG₃,CF₃—, —P(O)(C₆H₅)₂, —CO—G₃, —CO—NHG₃ or —CO—N(G₃)₂, G₃ is straight orbranched chain alkyl of 1 to 24 carbon atoms, straight or branched chainalkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or saidphenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4carbon atoms, E₁ is hydrogen, phenylalkyl of 7 to 15 carbon atoms,phenyl, or said phenyl or said phenylalkyl substituted on the phenylring by 1 to 4 alkyl of 1 to 4 carbon atoms, E₂ is straight or branchedalkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenylof 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkylof 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkylsubstituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms;or E₂ is hydroxyl or —OE₄ where E₄ is straight or branched chain alkylof 1 to 24 carbon atoms; or said alkyl substituted by one or more —OH,—OCO—E₁₁, —OE₄, —NCO or —NH₂ groups or mixtures thereof; or said alkylor said alkenyl interrupted by one or more —O—, —NH— or —NE₄— groups ormixtures thereof and which can be unsubstituted or substituted by one ormore —OH, —OE₄ or —NH₂ groups or mixtures thereof; or E₂ is —SE₃, —NHE₃or —N(E₃)₂; or E₂ is (CH₂)_(m)—CO—X—(Z)_(p)—Y—E₁₅ wherein X is —O— or—N(E₁₆)—, Y is —O— or —N(E₁₇)—, Z is C₂-C₁₂-alkylene, C₄-C₁₂-alkyleneinterrupted by one to three nitrogen atoms, oxygen atoms or a mixturethereof, or is C₃-C₁₂-alkylene, butenylene, butynylene, cyclohexylene orphenylene, each substituted by a hydroxyl group, m is zero, 1 or 2, p is1, or p is also zero when X and Y are —N(E₁₆)— and —N(E₁₇)—,respectively, E₁₅ is a group —CO—C(E₁₈)═C(H)E₁₉ or, when Y is —N(E₁₇)—,forms together with E₁₇ a group —CO—CH═CH—CO—, wherein E₁₈ is hydrogenor methyl, and E₁₉ is hydrogen, methyl or —CO—X—E₂₀, wherein E₂₀ ishydrogen, C₁-C₁₂-alkyl or a group of the formula.

wherein the symbols E₁, G₂, X, Z, m and p have the meanings definedabove, and E₁₆ and E₁₇ independently of one another are hydrogen,C₁-C₁₂-alkyl, C₃-C₁₂-alkyl interrupted by 1 to 3 oxygen atoms, or iscyclohexyl or C₇-C₁₅aralkyl, and E₁₆ together with E₁₇ in the case whereZ is ethylene, also forms ethylene, n is 1 or 2, when n is 1, E₅ is Cl,OE₆ or NE₇E₈, or E₅ is —PO(OE₁₂)₂, —OSi(E₁₁)₃ or —OCO—E₁₁, or straightor branched chain C₁-C₂₄alkyl which is interrupted by —O—, —S— or —NE₁₁and which can be unsubstituted or substituted by —OH or —OCO—E₁₁, C₅-C₁₂cycloalkyl which is unsubstituted or substituted by —OH, straight chainor branched C₂-C₁₈alkenyl which is unsubstituted or substituted by —OH,C₇-C₁₅aralkyl, —CH₂—CHOH—E₁₃ or glycidyl, E₆ is hydrogen, straight orbranched chain C₁-C₂₄alkyl which is unsubstituted or substituted by oneor more OH, OE₄ or NH₂ groups, or —OE₆ is —(OCH₂CH₂)_(w)OH or—(OCH₂CH₂)_(w)OE₂₁ where w is 1 to 12 and E₂₁ is alkyl of 1 to 12 carbonatoms, E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms, straight or branched chain C₃-C₁₈alkyl which is interrupted by—O—, —S— or —NE₁₁—, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl,or E₇ and E₈ together with the N atom are a pyrrolidine, piperidine,piperazine or morpholine ring, when n is 2, E₅ is one of divalentradicals —O—E₉—O— or —N(R₁₁)—E₁₀—N(E₁₁)—, E₉ is C₂-C₈alkylene,C₄-C₈alkenylene, C₄alkynylene, cyclohexylene, straight or branched chainC₄-C₁₀alkylene which is interrupted by —O— or by—CH₂—CHOH—CH₂—O—E₁₄—O—CH₂—CHOH—CH₂—, E₁₀ being straight or branchedchain C₂-C₁₂alkylene which may be interrupted by —O—, cyclohexylene, or

or E₁₀ and E₁₁ with the two nitrogen atoms form a piperazine ring, E₁₄is straight or branched chain C₂-C₈alkylene, straight or branched chainC₄-C₁₀alkylene which is interrupted by —O—, cycloalkylene, arylene or

where E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms or E₇ and E₈ together are alkylene of 4 to 6 carbon atoms,3-oxapentamethylene, 3-iminopentamethylene or3-methyliminopentamethylene, E₁₁ is hydrogen, straight or branched chainC₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, straight or branched chain C₃-C₈alkenyl,C₆-C₁₄aryl or C₇-C₁₅aralkyl, E₁₂ is straight or branched chainC₁-C₁₈alkyl, straight or branched chain C₃-C₁₈alkenyl, C₅-C₁₀cycloalkyl,C₆-C₁₆aryl or C₇-C₁₅aralkyl, E₁₃ is H, straight chain or branchedC₁-C₁₈alkyl which is substituted by —PO(OR₁₂)₂, phenyl which isunsubstituted or substituted by OH, C₇-C₁₅aralkyl or —CH₂OE₁₂, E₃ isalkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms,alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms orsaid aryl substituted by one or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms, L is alkylene of 1 to 12 carbon atoms, alkylidene of2 to 12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and Tis —SO—, —SO₂—, —SO—E—SO—, —SO₂—E—SO₂—, —CO—, —CO—E—CO—, —COO—E—OCO— or—CO—NG₅—E—NG₅—CO—, where E is alkylene of 2 to 12 carbon atoms,cycloalkylene of 5 to 12 carbon atoms, or alkylene interrupted orterminated by cyclohexylene of 8 to 12 carbon atoms; G₅ is G₃ orhydrogen, and with the proviso that E₁ is not phenylalkyl when G₂ isE₃SO— or E₃SO₂—.
 13. A compound according to claim 12 which is acompound of formula I′

wherein G₂ is cyano, E₃SO₂—, CF₃—, —COO—G₃—CO—NHG₃ or —CO—N(G₃)₂, G₃ isalkyl of 1 to 12 carbon atoms, E₁ is hydrogen, phenyl, phenylalkyl of 7to 15 carbon atoms or said phenyl or said phenylalkyl substituted on thephenyl ring by 1 or 2 alkyl groups of 1 to 4 carbon atoms, E₂ is alkylof 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon atoms or—CH₂CH₂COOG₄ where G₄ is hydrogen, alkyl of 1 to 24 carbon atoms or saidalkyl substituted by OH, interrupted by one to six —O— atoms or bothsubstituted by OH and interrupted by one to six —O— atoms, E₃ is alkylof 8 to 18 carbon atom, aryl of 6 to 10 carbon atoms or said arylsubstituted one or two alkyl of 1 to 4 carbon atoms, and with theproviso that E₁ is not phenylalkyl when G₂ is E₃SO— or E₃SO₂—.
 14. Acompound according to claim 13 wherein G₂ is cyano, E₃SO₂—, CF₃—, —CO—G₃or —CO—N(G₃)₂, G₃ is alkyl of 1 to 8 carbon atoms, E₁ is hydrogen,phenyl or α-cumyl, E₂ is alkyl of 4 to 12 carbon atoms, and E₃ is phenylor octyl, and with the proviso that E₁ is not α-cumyl when G₂ is E₃SO₂—.15. A compound according to claim 14 wherein G₂ is CF₃—, E₁ is α-cumyl,and E₂ is tert-butyl or tert-octyl.
 16. A composition stabilized againstthermal, oxidative or light-induced degradation which comprises, (a) anorganic material subject to thermal, oxidative or light-induceddegradation, and (b) an effective stabilizing amount of a compound offormula I, II, III or IV according to claim 12 .
 17. A compositionaccording to claim 16 wherein the organic material is a natural,semi-synthetic or synthetic polymer.
 18. A composition according toclaim 17 wherein the polymer is a thermoplastic polymer.
 19. Acomposition according to claim 18 wherein the polymer is is a polyolefinor polycarbonate.
 20. A composition according to claim 19 wherein thepolymer is polyethylene or polypropylene.
 21. A composition according toclaim 20 wherein the polymer is polypropylene.
 22. A compositionaccording to claim 16 wherein the organic material is a resin selectedfrom the group consisting of a thermoset acrylic melamine resin, anacrylic urethane resin, an epoxy carboxy resin, a silane modifiedacrylic melamine, an acrylic resin with carbamate pendant groupscrosslinked with melamine or an acrylic polyol resin crosslinked withmelamine containing carbamate groups.
 23. A composition according toclaim 22 wherein the resin is a thermoset acrylic melamine resin or anacrylic urethane resin.
 24. A composition according to claim 16 whereinthe organic material is a recording material.